Method for manufacturing semiconductor device

ABSTRACT

The semiconductor device is manufactured by the following method. A first oxide semiconductor film is formed over a first gate electrode and a first insulating film, oxygen is added to the first oxide semiconductor film, and then a second oxide semiconductor film is formed over the first oxide semiconductor film. Then, heat treatment is performed. Next, part of the first insulating film, part of the first oxide semiconductor film, and part of the second oxide semiconductor film are etched to form a first gate insulating film having a projection. Next, a pair of electrodes is formed over the second oxide semiconductor film, and a third oxide semiconductor film is formed over the second oxide semiconductor film and the pair of electrodes. Then, a second gate insulating film is formed over the third oxide semiconductor film, and a second gate electrode is formed over the second gate insulating film.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an object, a process (including a method and a manufacturing method), a machine, a manufacture, or a composition of matter. In particular, one embodiment of the present invention relates to a semiconductor device, a display device, a light-emitting device, a driving method thereof, a manufacturing method thereof, or the like. In particular, one embodiment of the present invention relates to a semiconductor device, a display device, a memory device, a light-emitting device, or the like including an oxide semiconductor.

In this specification, a semiconductor device refers to a device which can function by utilizing electronic characteristics of a semiconductor in its category, and for example, a semiconductor circuit is an example of the semiconductor device. Moreover, an electro-optic device, a display device, and an electric appliance may include a semiconductor device.

2. Description of the Related Art

Transistors used for most flat panel displays typified by a liquid crystal display device and a light-emitting display device are formed using silicon semiconductors such as amorphous silicon, single crystal silicon, and polycrystalline silicon provided over glass substrates. Further, transistors formed using such silicon semiconductors are used in integrated circuits (ICs) and the like.

In recent years, attention has been drawn to a technique in which, instead of a silicon semiconductor, a metal oxide exhibiting semiconductor characteristics is used for transistors. Note that in this specification, a metal oxide exhibiting semiconductor characteristics is referred to as an oxide semiconductor.

For example, a technique in which a transistor is manufactured using zinc oxide or an In—Ga—Zn-based oxide as an oxide semiconductor and the transistor is used as a switching element or the like of a pixel of a display device, is disclosed (see Patent Documents 1 and 2).

REFERENCE Patent Document

-   [Patent Document 1] Japanese Published Patent Application No.     2007-123861 -   [Patent Document 2] Japanese Published Patent Application No.     2007-096055

SUMMARY OF THE INVENTION

In a transistor using an oxide semiconductor, oxygen vacancies which are one cause of localized states in an oxide semiconductor film lead to poor electrical characteristics of the transistor.

In view of this, an object of one embodiment of the present invention is to improve electrical characteristics of a semiconductor device using an oxide semiconductor. Another object of one embodiment of the present invention is to improve reliability of a semiconductor device using an oxide semiconductor. Another object of one embodiment of the present invention is to reduce oxygen vacancies in an oxide semiconductor. Another object of one embodiment of the present invention is to prevent a transistor from becoming normally-on. Another object of one embodiment of the present invention is to control change, variation, or decrease in the threshold voltage of a transistor. Another object of one embodiment of the present invention is to provide a transistor having low off-state current. Another object of one embodiment of the present invention is to provide a novel semiconductor device or the like.

Note that the descriptions of these objects do not disturb the existence of other objects. Note that there is no need to achieve all of these objects with one embodiment of the present invention. Other objects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.

One embodiment of the present invention is a transistor including a first oxide semiconductor film, a second oxide semiconductor film, a pair of electrodes in contact with the second oxide semiconductor film, and a third oxide semiconductor film in contact with the second oxide semiconductor film and the pair of electrodes, in which oxygen is added to the first oxide semiconductor film or the third oxide semiconductor film to reduce oxygen vacancies. Further, the oxygen is diffused to the second oxide semiconductor film by heat treatment or the like, so that oxygen vacancies in the second oxide semiconductor film are reduced.

One embodiment of the present invention is a method for manufacturing a semiconductor device including the following steps. First, a first oxide semiconductor film is formed over a first gate electrode and a first insulating film provided over a substrate. Oxygen is added to the first oxide semiconductor film, and then a second oxide semiconductor film is formed over the first oxide semiconductor film. Furthermore, heat treatment is performed to transfer part of oxygen contained in the first oxide semiconductor film to the second oxide semiconductor film. Next, part of the first insulating film, part of the first oxide semiconductor film to which oxygen is added, and part of the second oxide semiconductor film to which oxygen is added are etched to form a first gate insulating film having a projection, the etched first oxide semiconductor film, and the etched second oxide semiconductor film. Next, a pair of electrodes is formed over the etched second oxide semiconductor film, and a third oxide semiconductor film is formed over the etched second oxide semiconductor film and the pair of electrodes. Next, a second gate insulating film is formed over the third oxide semiconductor film, and a second gate electrode is formed over the second gate insulating film.

One embodiment of the present invention is a method for manufacturing a semiconductor device including the following steps. First, a first oxide semiconductor film is formed over a first gate electrode and a first insulating film provided over a substrate. Then, a second oxide semiconductor film is formed over the first oxide semiconductor film. Next, part of the first insulating film, part of the first oxide semiconductor film, and part of the second oxide semiconductor film are etched to form a first gate insulating film having a projection, the etched first oxide semiconductor film, and the etched second oxide semiconductor film. Next, a pair of electrodes is formed over the etched second oxide semiconductor film, and a third oxide semiconductor film is formed over the etched second oxide semiconductor film and the pair of electrodes. Next, oxygen is added to the third oxide semiconductor film, and then heat treatment is performed to transfer part of oxygen contained in the third oxide semiconductor film to the etched second oxide semiconductor film. Next, a second gate insulating film is formed over the third oxide semiconductor film to which oxygen is added, and a second gate electrode is formed over the second gate insulating film.

Note that by adding oxygen to the first oxide semiconductor film and/or the third oxide semiconductor film and then performing heat treatment, oxygen vacancies in the first oxide semiconductor film and/or the third oxide semiconductor film can be reduced.

Note that the second oxide semiconductor film is an oxide semiconductor film containing In or Ga and is typically an In—Ga oxide film, an In—Zn oxide film, an In—Mg oxide film, a Zn—Mg oxide film, or an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd). Note that the element M is a metal element whose strength of bonding with oxygen is higher than that of In.

Furthermore, the first oxide semiconductor film and the third oxide semiconductor film are typically each an In—Ga oxide film, an In—Zn oxide film, an In—Mg oxide film, a Zn—Mg oxide film, or an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd), and has the energy level at the conduction band minimum that is closer to a vacuum level than that of the second oxide semiconductor film is. Typically, a difference between the energy level at the conduction band minimum of the second oxide semiconductor film and the energy level at the conduction band minimum of each of the first and third oxide semiconductor films is greater than or equal to 0.05 eV, greater than or equal to 0.07 eV, greater than or equal to 0.1 eV, or greater than or equal to 0.2 eV and also less than or equal to 2 eV, less than or equal to 1 eV, less than or equal to 0.5 eV, or less than or equal to 0.4 eV. Note that the difference between the vacuum level and the energy at the conduction band minimum is referred to as electron affinity.

Further, in the case where the first and third oxide semiconductor films and the second oxide semiconductor film are each an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd), the proportion of M atoms (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd) in each of the first and third oxide semiconductor films is higher than that in the second oxide semiconductor film. Typically, the proportion of M in each of the first and third oxide semiconductor films is higher than or equal to 1.5 times, preferably higher than or equal to twice, further preferably higher than or equal to three times as high as that in the second oxide semiconductor film.

As a method for adding oxygen to the first oxide semiconductor film or the third oxide semiconductor film, an ion implantation method, an ion doping method, plasma treatment, or the like can be used. The oxygen added to the first oxide semiconductor film or the third oxide semiconductor film is at least one kind selected from oxygen radicals, oxygen atoms, oxygen atomic ions, oxygen molecular ions, and the like.

With one embodiment of the present invention, electrical characteristics of a semiconductor device using an oxide semiconductor can be improved. With one embodiment of the present invention, reliability of a semiconductor device using an oxide semiconductor can be improved. Furthermore, with one embodiment of the present invention, a novel semiconductor device or the like can be provided. Note that the description of these effects does not disturb the existence of other effects. One embodiment of the present invention does not necessarily have all the effects listed above. Other effects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIGS. 1A to 1C are a top view and cross-sectional views illustrating one embodiment of a semiconductor device;

FIGS. 2A to 2D are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 3A to 3C are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 4A and 4B each show a band structure of a transistor;

FIGS. 5A to 5C are each a cross-sectional view of an embodiment of a semiconductor device;

FIGS. 6A to 6D are a top view and cross-sectional views illustrating one embodiment of a semiconductor device;

FIGS. 7A to 7C are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 8A to 8C are a top view and cross-sectional views illustrating one embodiment of a semiconductor device;

FIGS. 9A to 9C are a top view and cross-sectional views illustrating one embodiment of a semiconductor device;

FIGS. 10A to 10D are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 11A to 11C are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 12A to 12C are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 13A to 13C are cross-sectional views each illustrating an embodiment of a semiconductor device;

FIGS. 14A to 14C are a top view and cross-sectional views illustrating one embodiment of a semiconductor device;

FIGS. 15A to 15C are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 16A to 16C are cross-sectional views illustrating one embodiment of a method for manufacturing a semiconductor device;

FIGS. 17A to 17D are Cs-corrected high-resolution TEM images of a cross section of a CAAC-OS and a cross-sectional schematic view of a CAAC-OS;

FIGS. 18A to 18D are Cs-corrected high-resolution TEM images of a plane of a CAAC-OS;

FIGS. 19A to 19C show structure analysis of a CAAC-OS and a single crystal oxide semiconductor by XRD;

FIGS. 20A and 20B are a cross-sectional view and a circuit diagram of one embodiment of a semiconductor device;

FIGS. 21A to 21F each illustrate an electronic device that uses one embodiment of the present invention;

FIG. 22 shows the calculation results of the oxygen concentration;

FIG. 23 shows SIMS measurement results;

FIG. 24 shows SIMS measurement results;

FIGS. 25A to 25C show electrical characteristics of transistors;

FIG. 26 shows the amount of changes in the threshold voltage and the shift value of a transistor;

FIG. 27 shows the calculation results of the oxygen concentration;

FIG. 28 is a cross-sectional view illustrating one embodiment of a semiconductor device;

FIG. 29 illustrates a data writing operation and a data reading operation of a memory cell;

FIGS. 30A to 30C are a schematic diagram and circuit diagrams of a display device;

FIG. 31 illustrates a display module;

FIGS. 32A and 32B are cross-sectional views each illustrating one embodiment of a semiconductor device;

FIGS. 33A to 33D are cross-sectional views each illustrating one embodiment of a semiconductor device;

FIGS. 34A to 34D are cross-sectional views each illustrating one embodiment of a semiconductor device;

FIGS. 35A and 35B show electron diffraction patterns of a CAAC-OS;

FIG. 36 shows a change of crystal parts of an In—Ga—Zn oxide by electron irradiation;

FIGS. 37A and 37B are schematic diagrams illustrating deposition models of a CAAC-OS and an nc-OS;

FIGS. 38A to 38C illustrate an InGaZnO₄ crystal and a pellet; and

FIGS. 39A to 39D are schematic diagrams illustrating a deposition model of a CAAC-OS.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will be described below in detail with reference to the drawings. Note that the present invention is not limited to the following description. It will be readily appreciated by those skilled in the art that modes and details of the present invention can be changed in various ways without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the following description of the embodiments. In addition, in the following embodiments and examples, the same portions or portions having similar functions are denoted by the same reference numerals or the same hatching patterns in different drawings, and description thereof will not be repeated.

Note that in each drawing described in this specification, the size, the film thickness, or the region of each component is exaggerated for clarity in some cases. Therefore, embodiments of the present invention are not limited to such a scale.

In addition, terms such as “first”, “second”, and “third” in this specification are used in order to avoid confusion among components, and the terms do not limit the components numerically. Therefore, for example, the term “first” can be replaced with the term “second”, “third”, or the like as appropriate.

Note that, functions of “source” and “drain” may be switched in the case where the direction of a current flow is changed during circuit operation, for example. Therefore, the terms “source” and “drain” can be used to denote the drain and the source, respectively, in this specification.

The term “parallel” indicates that the angle formed between two straight lines is greater than or equal to −10° and less than or equal to 10°, and accordingly also includes the case where the angle is greater than or equal to −5° and less than or equal to 5°. The term “perpendicular” indicates that the angle formed between two straight lines is greater than or equal to 80° and less than or equal to 100°, and accordingly also includes the case where the angle is greater than or equal to 85° and less than or equal to 95°.

In this specification, trigonal and rhombohedral crystal systems are included in a hexagonal crystal system.

Note that a voltage refers to a difference between potentials of two points, and a potential refers to electrostatic energy (electric potential energy) of a unit charge at a given point in an electrostatic field. Note that in general, a difference between a potential of one point and a reference potential (e.g., a ground potential) is merely called a potential or a voltage, and a potential and a voltage are used as synonymous words in many cases. Thus, in this specification, a potential may be rephrased as a voltage and a voltage may be rephrased as a potential unless otherwise specified.

Note that a transistor including an oxide semiconductor film is an n-channel transistor; therefore, in this specification, a transistor which can be regarded as having no drain current flowing therein when a gate voltage is 0 V is defined as a transistor having normally-off characteristics. In contrast, a transistor which can be regarded as having a drain current flowing therein when the gate voltage is 0 V is defined as a transistor having normally-on characteristics.

Note that in this specification, the channel length refers to, for example, a distance between a source (a source region or a source electrode) and a drain (a drain region or a drain electrode) in a region where an oxide semiconductor film (or a portion where a current flows in an oxide semiconductor film when a transistor is on) and a gate electrode overlap with each other or a region where a channel is formed in a top view of the transistor. In one transistor, channel lengths in all regions are not necessarily the same. In other words, the channel length of one transistor is not limited to one value in some cases. Therefore, in this specification, the channel length is any one of values, the maximum value, the minimum value, or the average value in a region where a channel is formed.

The channel width refers to, for example, the length of a portion where a source and a drain face each other in a region where an oxide semiconductor film (or a portion where a current flows in an oxide semiconductor film when a transistor is on) and a gate electrode overlap with each other, or a region where a channel is formed. In one transistor, channel widths in all regions are not necessarily the same. In other words, the channel width of one transistor is not limited to one value in some cases. Therefore, in this specification, the channel width is any one of values, the maximum value, the minimum value, or the average value in a region where a channel is formed.

Note that depending on transistor structures, a channel width in a region where a channel is formed actually (hereinafter referred to as an effective channel width) is different from a channel width shown in a top view of a transistor (hereinafter referred to as an apparent channel width) in some cases. For example, in a transistor having a three-dimensional structure, an effective channel width is greater than an apparent channel width shown in a top view of the transistor, and its influence cannot be ignored in some cases. For example, in a miniaturized transistor having a three-dimensional structure, the proportion of a channel region formed in a side surface of an oxide semiconductor film is higher than the proportion of a channel region formed in a top surface of an oxide semiconductor film in some cases. In that case, an effective channel width obtained when a channel is actually formed is greater than an apparent channel width shown in the top view.

In a transistor having a three-dimensional structure, an effective channel width is difficult to measure in some cases. For example, to estimate an effective channel width from a design value, it is necessary to assume that the shape of an oxide semiconductor film is known. Therefore, in the case where the shape of an oxide semiconductor film is not known accurately, it is difficult to measure an effective channel width accurately.

In view of the above, in a top view of a transistor, an apparent channel width that is a length of a portion where a source and a drain face each other in a region where an oxide semiconductor film and a gate electrode overlap with each other may be referred to as a “surrounded channel width (SCW)” in this specification. Further, in this specification, in the case where the term “channel width” is simply used, it may denote a surrounded channel width and an apparent channel width. Alternatively, in this specification, in the case where the term “channel width” is simply used, it may denote an effective channel width in some cases. Note that the values of a channel length, a channel width, an effective channel width, an apparent channel width, a surrounded channel width, and the like can be determined by obtaining and analyzing a cross-sectional TEM image and the like.

Note that in the case where electric field mobility, a current value per channel width, and the like of a transistor are obtained by calculation, a surrounded channel width may be used for the calculation. In that case, a value different from one in the case where an effective channel width is used for the calculation is obtained in some cases.

Embodiment 1

The threshold voltage of a transistor using an oxide semiconductor film with oxygen vacancies easily shifts in the negative direction, and such a transistor tends to be normally-on. This is because electric charges are generated owing to oxygen vacancies in the oxide semiconductor, and the resistance is reduced. In addition, a transistor using an oxide semiconductor film with oxygen vacancies has such a problem that the electrical characteristics, typically, the threshold voltage, are changed with time or changed by a stress test (typically, a gate bias-temperature (BT) stress test under light irradiation). In this embodiment, a highly reliable semiconductor device in which a change in threshold voltage is small and a manufacturing method thereof will be described. Further, a semiconductor device with excellent electrical characteristics and a manufacturing method thereof will be described.

<Structure Example of Semiconductor Device>

In this embodiment, a method for manufacturing a top-gate transistor is described.

FIGS. 1A to 1C are a top view and cross-sectional views of a transistor 100 of a semiconductor device. FIG. 1A is a top view of the transistor 100, FIG. 1B is a cross-sectional view taken along dashed-dotted line A-B in FIG. 1A, and FIG. 1C is a cross-sectional view taken along dashed-dotted line C-D in FIG. 1A. Note that in FIG. 1A, a substrate 101, a gate insulating film 105, an oxide semiconductor film 107, an oxide semiconductor film 115, a gate insulating film 117, an insulating film 121, an insulating film 123, and the like are not illustrated for simplicity.

FIG. 1B is a cross-sectional view in the channel length direction of the transistor 100 and FIG. 1C is a cross-sectional view in the channel width direction of the transistor 100.

The transistor 100 illustrated in FIGS. 1A to 1C is provided over the substrate 101. The transistor 100 includes a gate electrode 103 over the substrate 101, the gate insulating film 105 over the substrate 101 and the gate electrode 103, the oxide semiconductor film 107 in contact with the gate insulating film 105, an oxide semiconductor film 111 in contact with a top surface of the oxide semiconductor film 107, a pair of electrodes 113 a and 113 b in contact with at least a top surface and a side surface of the oxide semiconductor film 111 and a side surface of the oxide semiconductor film 107, the oxide semiconductor film 115 in contact with the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b, the gate insulating film 117 overlapping with the oxide semiconductor film 111 with the oxide semiconductor film 115 sandwiched therebetween, and a gate electrode 119 being in contact with the gate insulating film 117 and overlapping with the oxide semiconductor film 111 with the oxide semiconductor film 115 and the gate insulating film 117 sandwiched therebetween. Furthermore, the insulating film 121 that covers the pair of electrodes 113 a and 113 b, the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119 and the insulating film 123 that covers the insulating film 121 may be included.

Note that at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is provided on at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is in contact with at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111). Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is in contact with at least part (or the whole) of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is electrically connected to at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111). Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is electrically connected to part (or the whole) of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned close to at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111). Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned close to part (or the whole) of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned beside at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111). Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned beside part (or the whole) of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned diagonally above at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111). Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned diagonally above part (or the whole) of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned above at least part (or the whole) of a surface, a side surface, a top surface, and/or a bottom surface of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111). Alternatively, at least part (or the whole) of the electrode 113 a (and/or the electrode 113 b) is positioned above part (or the whole) of a semiconductor film such as the oxide semiconductor film 107 (and/or the oxide semiconductor film 111).

The transistor 100 includes two gate electrodes. One of them has a function of controlling on/off state of the transistor 100. The other has a function of controlling the threshold voltage of the transistor 100. By applying a voltage that makes the threshold voltage of the transistor 100 positive to one of the gate electrodes, the transistor 100 can have normally-off characteristics.

The gate insulating film 105 included in the transistor 100 has a projection. The oxide semiconductor films 107 and 111 are formed over the projection. In the channel width direction as illustrated in FIG. 1C, the gate electrode 119 faces side surfaces of the oxide semiconductor films 107 and 111 with the gate insulating film 117 positioned therebetween. In other words, when a voltage is applied to the gate electrode 119, the oxide semiconductor films 107 and 111 are surrounded by electric field of the gate electrode 119 in the channel width direction. The transistor structure in which an oxide semiconductor film is surrounded by electric field of a gate electrode is referred to as a surrounded channel (s-channel) structure. In the transistor with the s-channel structure, a channel is formed in the whole oxide semiconductor film 111 (bulk) in the on state; as a result, an on-state current is increased. In the off state, the entire region of the channel region formed in the oxide semiconductor film 111 is depleted; as a result, an off-state current can be further reduced.

Components of the transistor 100 are described below.

Although there is no particular limitation on a material and the like of the substrate 101, it is necessary that the substrate have heat resistance high enough to withstand at least heat treatment performed later. For example, a glass substrate, a ceramic substrate, a quartz substrate, a sapphire substrate, or the like may be used as the substrate 101. Alternatively, a single crystal semiconductor substrate or a polycrystalline semiconductor substrate made of silicon, silicon carbide, or the like, a compound semiconductor substrate made of silicon germanium or the like, an SOI substrate, or the like may be used as the substrate 101. Furthermore, any of these substrates provided with a semiconductor element may be used as the substrate 101. Alternatively, gallium arsenide, aluminum gallium arsenide, indium gallium arsenide, gallium nitride, indium phosphide, silicon germanium, or the like which can be employed for a high-electron-mobility transistor (HEMT) may be used as the material of the substrate 101. By using any of these semiconductors as the material of the substrate 101, the transistor 100 suited to high speed operation can be obtained. The substrate 101 is not limited to a simple supporting substrate, and may be a substrate where a device such as a transistor is formed. In this case, at least one of the gate electrode, the source electrode, and the drain electrode of the transistor 100 may be electrically connected to the device.

Note that a flexible substrate may also be used as the substrate 101. In the case where a flexible substrate is used, a transistor, a capacitor, or the like may be directly formed over the flexible substrate, or a transistor, a capacitor, or the like may be formed over a manufacturing substrate and then separated and transferred onto the flexible substrate. To perform separation and transfer from the manufacturing substrate to the flexible substrate, a separation layer may be provided between the manufacturing substrate and the transistor, the capacitor, or the like.

The gate electrode 103 has a function of controlling the threshold voltage of the transistor 100. The gate electrode 103 can be formed using a metal element selected from aluminum, chromium, copper, tantalum, titanium, molybdenum, manganese, and tungsten; an alloy containing any of these metal elements as a component; an alloy containing any of these metal elements in combination; or the like. Furthermore, one or more metal elements selected from manganese and zirconium may be used. Moreover, the gate electrode 103 may have a single-layer structure or a stacked structure of two or more layers. For example, the gate electrode 103 can have a single-layer structure of an aluminum film containing silicon, a single-layer structure of a copper film containing manganese, a two-layer structure in which a titanium film is stacked over an aluminum film, a two-layer structure in which a copper film is stacked over a copper-magnesium alloy film, a two-layer structure in which a titanium film is stacked over a titanium nitride film, a two-layer structure in which a tungsten film is stacked over a tantalum nitride film or a tungsten nitride film, a three-layer structure in which a titanium film, an aluminum film, and a titanium film are formed in this order, a three-layer structure in which a copper-magnesium alloy film, a copper film, and a copper-magnesium alloy film are stacked in this order, or the like. Alternatively, an alloy film or a nitride film which contains aluminum and one or more elements selected from titanium, tantalum, tungsten, molybdenum, chromium, neodymium, and scandium may be used.

The gate electrode 103 can also be formed using a light-transmitting conductive material such as indium tin oxide, indium oxide containing tungsten oxide, indium zinc oxide containing tungsten oxide, indium oxide containing titanium oxide, indium tin oxide containing titanium oxide, indium zinc oxide, or indium tin oxide to which silicon oxide is added. The gate electrode 103 can have a stacked structure formed using the above-described light-transmitting conductive material and the above-described metal element.

Note that it is preferable that element(s) included in the gate electrode 103 be not diffused to the gate insulating film 105. For example, when an alloy film which contains one or more elements selected from tungsten, tantalum, molybdenum, copper, titanium, and aluminum, an alloy film to which a small amount of element is added, or the like is used as the gate electrode 103, it is hard for element(s) included in the gate electrode 103 to be diffused into the gate insulating film 105.

As the gate electrode 103, an In—Ga—Zn-based oxynitride film, an In—Sn-based oxynitride film, an In—Ga-based oxynitride film, an In—Zn-based oxynitride film, a metal oxynitride film (e.g., SnON, InON), a metal nitride film (e.g., InN, ZnN), or the like may be provided. For example, in the case of using an In—Ga—Zn-based oxynitride film, an In—Ga—Zn-based oxynitride film whose nitrogen concentration is higher than at least the nitrogen concentration of the oxide semiconductor film 111, specifically, an In—Ga—Zn-based oxynitride film whose nitrogen concentration is higher than or equal to 7 at. % is used. In the case of forming the gate electrode 103 using any of the above-described metal oxynitride films or the metal nitride films, it is preferable to provide a protective film that prevents diffusion of metal, oxygen, or nitrogen over the gate electrode 103. Examples of the protective film are an alloy film containing one or more elements selected from tungsten, tantalum, molybdenum, copper, titanium, and aluminum, or an alloy film to which a small amount of element is added.

As the gate insulating film 105, a single layer or a stacked layer of, for example, a silicon oxide film, a silicon oxynitride film, a silicon nitride oxide film, a silicon nitride film, an aluminum oxide film, a hafnium oxide film, a gallium oxide film, a Ga—Zn-based metal oxide film, or the like can be provided. The gate insulating film 105 is preferably a film with a small number of defects or a small number of impurities in order to reduce variations in electrical characteristics of the transistor such as the threshold voltage.

It is possible to prevent outward diffusion of oxygen from an oxide semiconductor film 109 and entry of hydrogen, water, or the like into the oxide semiconductor film 109 from the outside by providing an insulating film having a blocking effect against oxygen, hydrogen, water, and the like as the gate insulating film 105. Examples of the insulating film having a blocking effect against oxygen, hydrogen, water, and the like are an aluminum oxide film, an aluminum oxynitride film, a gallium oxide film, a gallium oxynitride film, an yttrium oxide film, an yttrium oxynitride film, a hafnium oxide film, and a hafnium oxynitride film.

The gate insulating layer 105 may be formed using a high-k material such as hafnium silicate (HfSiO_(x)), hafnium silicate to which nitrogen is added (HfSi_(x)O_(y)N_(z)), hafnium aluminate to which nitrogen is added (HfAl_(x)O_(y)N_(z)), hafnium oxide, yttrium oxide, or aluminum oxide, so that gate leakage current of the transistor can be reduced.

The thickness of the gate insulating film 105 is greater than or equal to 5 nm and less than or equal to 400 nm, greater than or equal to 5 nm and less than or equal to 300 nm, or greater than or equal to 10 nm and less than or equal to 50 nm. By reducing the thickness of the gate insulating film 105, the voltage applied to the gate electrode 103 can be lowered, so that power consumption of the semiconductor device can be reduced.

The oxide semiconductor film 111 is an oxide semiconductor film containing In or Ga and typically an In—Ga oxide film, an In—Zn oxide film, an In—Mg oxide film, an Zn—Mg oxide film, or an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd).

Note that in the case where the oxide semiconductor film 111 is an In-M-Zn oxide film, the proportion of In and the proportion of M, not taking Zn and O into consideration, are preferably greater than 25 atomic % and less than 75 atomic %, respectively, further preferably greater than 34 atomic % and less than 66 atomic %, respectively.

The indium and gallium contents in the oxide semiconductor film 111 can be compared with each other by time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectrometry (XPS), or inductively coupled plasma mass spectrometry (ICP-MS).

Since the oxide semiconductor film 111 has an energy gap of 2 eV or more, preferably 2.5 eV or more, further preferably 3 eV or more, the off-state current of the transistor 100 can be low.

The thickness of the oxide semiconductor film 111 is greater than or equal to 3 nm and less than or equal to 200 nm, preferably greater than or equal to 3 nm and less than or equal to 100 nm, further preferably greater than or equal to 3 nm and less than or equal to 50 nm.

The oxide semiconductor film 107 and the oxide semiconductor film 115 are oxide semiconductor films containing one or more elements that are included in the oxide semiconductor film 111. Therefore, interface scattering is unlikely to occur at an interface between the oxide semiconductor film 111 and each of the oxide semiconductor films 107 and 115. Thus, the transistor 100 can have a high field-effect mobility because the movement of carriers is not hindered at the interfaces.

The oxide semiconductor film 107 and the oxide semiconductor film 115 are typically each an In—Ga oxide film, an In—Zn oxide film, an In—Mg oxide film, a Zn—Mg oxide film, or an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd), and has the energy level at the conduction band minimum that is closer to a vacuum level than that of the oxide semiconductor film 111 is. Typically, a difference between the energy level at the conduction band minimum of the oxide semiconductor film 111 and the energy level at the conduction band minimum of each of the oxide semiconductor films 107 and 115 is greater than or equal to 0.05 eV, greater than or equal to 0.07 eV, greater than or equal to 0.1 eV, or greater than or equal to 0.2 eV and also less than or equal to 2 eV, less than or equal to 1 eV, less than or equal to 0.5 eV, or less than or equal to 0.4 eV. That is, the difference between the electron affinity of the oxide semiconductor film 111 and the electron affinity of each of the oxide semiconductor films 107 and 115 is greater than or equal to 0.05 eV, greater than or equal to 0.07 eV, greater than or equal to 0.1 eV, or greater than or equal to 0.2 eV and also less than or equal to 2 eV, less than or equal to 1 eV, less than or equal to 0.5 eV, or less than or equal to 0.4 eV. Note that the electron affinity refers to an energy gap between the vacuum level and the conduction band minimum. The oxide semiconductor film 111 has a larger electron affinity than those of the oxide semiconductor film 107 and the oxide semiconductor film 115. For example, as the oxide semiconductor film 111, an oxide semiconductor film having an electron affinity higher than those of the oxide semiconductor films 107 and 115 by 0.07 eV or more and 1.3 eV or less, preferably 0.1 eV or more and 0.7 eV or less, further preferably 0.2 eV or more and 0.4 eV or less is used.

When the oxide semiconductor films 107 and 115 contain a larger amount of Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd in an atomic ratio than the amount of In in an atomic ratio, any of the following effects may be obtained.

(1) The energy gap of each of the oxide semiconductor films 107 and 115 is widened. (2) The electron affinity of each of the oxide semiconductor films 107 and 115 is reduced. (3) Impurities from the outside are blocked. (4) An insulating property of each of the oxide semiconductor films 107 and 115 is higher than that of the oxide semiconductor film 111. (5) Oxygen vacancies are less likely to be generated in the oxide semiconductor films 107 and 115 because Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, and Nd are metal elements that can be strongly bonded to oxygen.

Note that since the oxide semiconductor films 107 and 115 have higher insulating properties than the oxide semiconductor film 111, they each have a function of a gate insulating film.

In the case where the oxide semiconductor films 107 and 115 are each an In-M-Zn oxide film, the proportion of In and the proportion of M, not taking Zn and O into consideration, are less than 50 atomic % and greater than 50 atomic %, respectively, and preferably less than 25 atomic % and greater than 75 atomic %, respectively.

Further, in the case where the oxide semiconductor films 107, 111, and 115 are each an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd), the proportion of M atoms (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd) in each of the oxide semiconductor films 107 and 115 is higher than that in the oxide semiconductor film 111. Typically, the proportion of M in each of the oxide semiconductor films 107 and 115 is higher than or equal to 1.5 times, preferably higher than or equal to twice, further preferably higher than or equal to three times as high as that in the oxide semiconductor film 111. Any of the above-described elements represented by M is more strongly bonded to oxygen than indium is, and thus has a function of suppressing generation of oxygen vacancies in the oxide semiconductor films 107 and 115. That is, oxygen vacancies are less likely to be generated in the oxide semiconductor films 107 and 115 than in the oxide semiconductor film 111.

In the case where the oxide semiconductor film 111 is an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd) and a target having the atomic ratio of metal elements of In:M:Zn=x₁:y₁:z₁ is used for forming the oxide semiconductor film 111, x₁/y₁ is preferably greater than or equal to ⅓ and less than or equal to 6, further preferably greater than or equal to 1 and less than or equal to 6, and z₁/y₁ is preferably greater than or equal to ⅓ and less than or equal to 6, further preferably greater than or equal to 1 and less than or equal to 6. Note that when z₁/y₁ is greater than or equal to 1 and less than or equal to 6, a c-axis aligned crystalline oxide semiconductor (CAAC-OS) film as the oxide semiconductor film 111 can be easily formed. Typical examples of the atomic ratio of In to M and Zn of the target are 1:1:1, 1:1:1.2, 2:1:1.5, 2:1:2.3, 2:1:3, and 3:1:2.

In the case where the oxide semiconductor film 107 and the oxide semiconductor film 115 are each an In-M-Zn oxide film (M is Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, or Nd) and a target having the atomic ratio of metal elements of In:M:Zn=x₂:y₂:z₂ is used for forming the oxide semiconductor films 107 and 115, x₂/y₂ is preferably less than x₁/y₁, and z₂/y₂ is preferably greater than or equal to ⅓ and less than or equal to 6, further preferably greater than or equal to 1 and less than or equal to 6. Note that when z₂/y₂ is greater than or equal to 1 and less than or equal to 6, a CAAC-OS films as the oxide semiconductor films 107 and 115 can be easily formed. Typical examples of the atomic ratio of In to M and Zn of the target are 1:3:2, 1:3:4, 1:3:6, 1:3:8, 1:4:4, 1:4:5, 1:4:6, 1:4:7, 1:4:8, 1:5:5, 1:5:6, 1:5:7, 1:5:8, and 1:6:8.

In each of the oxide semiconductor films 107, 111, and 115, the proportion of each atom in the above-described atomic ratio varies within a range of ±40% as an error.

The atomic ratio is not limited to those described above, and may be appropriately set in accordance with needed semiconductor characteristics.

The oxide semiconductor film 107 and the oxide semiconductor film 115 may have the same atomic ratio of metal elements. For example, each of the oxide semiconductor film 107 and the oxide semiconductor film 115 may be an In—Ga—Zn oxide with an atomic ratio of In:Ga:Zn=1:3:2, 1:3:4, or 1:4:5.

Alternatively, the oxide semiconductor film 107 and the oxide semiconductor film 115 may have different atomic ratios of metal elements. For example, the oxide semiconductor film 107 may be an In—Ga—Zn oxide with an atomic ratio of In:Ga:Zn=1:3:2, and the oxide semiconductor film 115 may be an In—Ga—Zn oxide with an atomic ratio of In:Ga:Zn=1:3:4 or 1:4:5.

The oxide semiconductor film 107 and the oxide semiconductor film 115 may each have a thickness of more than or equal to 3 nm and less than or equal to 100 nm, or more than or equal to 3 nm and less than or equal to 50 nm.

Here, it is preferable that the thickness of the oxide semiconductor film 111 be at least larger than that of the oxide semiconductor film 107. The thicker the oxide semiconductor film 111 is, the larger the on-state current of the transistor can be. The thickness of the oxide semiconductor film 107 may be set as appropriate as long as formation of interface states at the interface with the oxide semiconductor film 111 can be inhibited. For example, the thickness of the oxide semiconductor film 111 is larger than that of the oxide semiconductor film 107, preferably 2 or more times, further preferably 4 or more times, still further preferably 6 or more times as large as that of the oxide semiconductor film 107. Note that the above description does not apply in the case where the on-state current of the transistor need not be increased, in which case the thickness of the oxide semiconductor film 107 may be larger than or equal to than that of the oxide semiconductor film 111. In this case, more oxygen can be added to the oxide semiconductor film 107, and oxygen vacancies in the oxide semiconductor film 111 can be reduced by heat treatment.

The thickness of the oxide semiconductor film 115 may be set as appropriate, in a manner similar to that of the oxide semiconductor film 107, as long as formation of interface states at the interface with the oxide semiconductor film 111 can be inhibited. For example, the thickness of the oxide semiconductor film 115 may be set smaller than or equal to that of the oxide semiconductor film 107. If the oxide semiconductor film 115 is thick, it may become difficult for the electric field from the gate electrode 103 to reach the oxide semiconductor film 111; thus, it is preferable that the oxide semiconductor film 115 be thin. In addition, to prevent oxygen contained in the oxide semiconductor film 115 from diffusing to the pair of electrodes 113 a and 113 b and thus oxidizing the pair of electrodes 113 a and 113 b, it is preferable that the oxide semiconductor film 115 be thin. Note that the thickness of the oxide semiconductor film 115 is not limited to the above, and may be set as appropriate in accordance with the driving voltage of the transistor in consideration of the withstand voltage of the gate insulating film 117.

In the case where the oxide semiconductor film 107, the oxide semiconductor film 111, and the oxide semiconductor film 115 have different compositions from one another, the interfaces thereof can be observed by scanning transmission electron microscopy (STEM).

Hydrogen contained in the oxide semiconductor films 107, 111, and 115 reacts with oxygen bonded to a metal atom to produce water, which causes oxygen vacancies in a lattice from which oxygen is released (or a portion from which oxygen is released). Electrons serving as carriers might be generated when hydrogen enters the oxygen vacancies. Further, electrons serving as carriers might be generated when part of hydrogen is bonded to oxygen bonded to a metal atom. Thus, a transistor including an oxide semiconductor which contains hydrogen is likely to be normally on.

Accordingly, it is preferable that hydrogen be reduced as much as possible as well as the oxygen vacancies in the oxide semiconductor films 107, 111, and 115. Specifically, the hydrogen concentration of the oxide semiconductor films 107, 111, and 115, which is measured by secondary ion mass spectrometry (SIMS), is lower than or equal to 5×10¹⁹ atoms/cm³, lower than or equal to 1×10¹⁹ atoms/cm³, lower than or equal to 5×10¹⁸ atoms/cm³, lower than or equal to 1×10¹⁸ atoms/cm³, lower than or equal to 5×10¹⁷ atoms/cm³, or lower than or equal to 1×10¹⁶ atoms/cm³. As a result, the transistor 100 has positive threshold voltage (normally-off characteristics).

Note that the impurity concentration of the oxide semiconductor films 107, 111, and 115 can be measured by secondary ion mass spectrometry (SIMS).

When the oxide semiconductor films 107, 111, and 115 contain silicon or carbon that is a Group 14 element, oxygen vacancies in the films increase to form n-type regions. Thus, the concentration of silicon or carbon (the concentration is measured by SIMS) of each of the oxide semiconductor films 107, 111, and 115 is set lower than or equal to 2×10¹⁸ atoms/cm³, preferably lower than or equal to 2×10¹⁷ atoms/cm³. As a result, the transistor 100 has positive threshold voltage (normally-off characteristics).

Furthermore, the concentration of alkali metal or alkaline earth metal of the oxide semiconductor films 107, 111, and 115, which is measured by SIMS, is set lower than or equal to 1×10¹⁸ atoms/cm³, preferably lower than or equal to 2×10¹⁶ atoms/cm³. Alkali metal and alkaline earth metal might generate carriers when bonded to an oxide semiconductor, which may increase the off-state current of the transistor. Thus, it is preferable to reduce the concentration of alkali metal or alkaline earth metal of the oxide semiconductor films 107, 111, and 115. As a result, the transistor 100 has positive threshold voltage (normally-off characteristics).

Further, when containing nitrogen, the oxide semiconductor films 107, 111, and 115 easily become n-type by generation of electrons serving as carriers and an increase of carrier density. Thus, a transistor including an oxide semiconductor which contains nitrogen is likely to be normally on. For this reason, nitrogen in the oxide semiconductor film is preferably reduced as much as possible; the concentration of nitrogen which is measured by SIMS is preferably set, for example, lower than or equal to 5×10¹⁸ atoms/cm³.

When impurities in the oxide semiconductor films 107, 111, and 115 are reduced, the carrier density of the oxide semiconductor films can be lowered. The oxide semiconductor films 107, 111, and 115 preferably have a carrier density of 1×10¹⁷/cm³ or less, preferably 1×10¹⁵/cm³ or less, preferably 1×10¹³/cm³ or less, preferably 8×10¹¹/cm³ or less, further preferably 1×10¹¹/cm³ or less, further preferably less than 1×10¹⁰/cm³, and is 1×10⁻⁹/cm³ or more.

Note that an oxide semiconductor film with a low impurity concentration and a low density of defect states can be used for the oxide semiconductor films 107, 111, and 115, in which case the transistor can have more excellent electrical characteristics. Here, the state in which the impurity concentration is low and the density of defect states is low (the number of oxygen vacancies is small) is described as “highly purified intrinsic” or “substantially highly purified intrinsic.” A highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor has few carrier generation sources, and thus has a low carrier density in some cases. Thus, a transistor including the oxide semiconductor film in which a channel region is formed is likely to have positive threshold voltage (normally-off characteristics). A highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor film has a low density of defect states and accordingly has few carrier traps in some cases. Further, a highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor film has an extremely low off-state current; the off-state current can be less than or equal to the measurement limit of a semiconductor parameter analyzer, i.e., less than or equal to 1×10⁻¹³ A, at a voltage between a source electrode and a drain electrode (drain voltage) of from 1 V to 10 V. Thus, the transistor whose channel region is formed in the oxide semiconductor film has a small variation in electrical characteristics and high reliability in some cases.

The oxide semiconductor films 107, 111, and 115 may have a non-single crystal structure, for example. The non-single crystal structure includes a CAAC-OS which is described later, a polycrystalline structure, a microcrystalline structure, or an amorphous structure, for example. Among the non-single crystal structure, the amorphous structure has the highest density of defect states, whereas the CAAC-OS has the lowest density of defect states.

The oxide semiconductor films 107, 111, and 115 may have a microcrystalline structure, for example. The oxide semiconductor films 107, 111, and 115 which have the microcrystalline structure each include a microcrystal with a size greater than or equal to 1 nm and less than 10 nm, for example. Alternatively, the oxide semiconductor films which have the microcrystalline structure have a mixed phase structure where crystal parts (each of which is greater than or equal to 1 nm and less than 10 nm) are distributed in an amorphous phase.

The oxide semiconductor films 107, 111, and 115 may have an amorphous structure, for example. The oxide semiconductor films 107, 111, and 115 which have the amorphous structure each have disordered atomic arrangement and no crystalline component, for example. Alternatively, the oxide semiconductor films which have an amorphous structure have, for example, an absolutely amorphous structure and no crystal part.

Note that the oxide semiconductor films 107, 111, and 115 may each be a mixed film including regions having two or more of the following structures: a CAAC-OS, a microcrystalline structure, and an amorphous structure. The mixed film, for example, has a single-layer structure including a region having an amorphous structure, a region having a microcrystalline structure, and a region of a CAAC-OS. Alternatively, the mixed film may have a stacked-layer structure including a region having an amorphous structure, a region having a microcrystalline structure, and a region of a CAAC-OS, for example.

Note that the oxide semiconductor films 107, 111, and 115 may have a single-crystal structure, for example.

By providing an oxide semiconductor film in which oxygen vacancies are less likely to be generated than in the oxide semiconductor film 111, over and under and in contact with the oxide semiconductor film 111, oxygen vacancies in the oxide semiconductor film 111 can be reduced. Further, since the oxide semiconductor film 111 is in contact with the oxide semiconductor films 107 and 115 containing one or more metal elements forming the oxide semiconductor film 111, the density of interface states at the interface between the oxide semiconductor film 107 and the oxide semiconductor film 111 and at the interface between the oxide semiconductor film 111 and the oxide semiconductor film 115 is extremely low. Thus, after oxygen is added to the oxide semiconductor films 107 and 115, the oxygen is transferred from the oxide semiconductor films 107 and 115 to the oxide semiconductor film 111 by heat treatment; however, the oxygen is hardly trapped by the interface states at this time, and the oxygen in the oxide semiconductor films 107 and 115 can be efficiently transferred to the oxide semiconductor film 111. Accordingly, oxygen vacancies in the oxide semiconductor film 111 can be reduced. Since oxygen is added to the oxide semiconductor films 107 and 115, oxygen vacancies in the oxide semiconductor films 107 and 115 can be reduced. In other words, the density of localized states of at least the oxide semiconductor film 111 can be reduced.

In addition, when the oxide semiconductor film 111 is in contact with an insulating film including a different constituent element (e.g., a gate insulating film including a silicon oxide film), an interface state is sometimes formed and the interface state forms a channel. At this time, a second transistor having a different threshold voltage appears, so that an apparent threshold voltage of the transistor is varied. However, since the oxide semiconductor films 107 and 115 containing one or more kinds of metal elements forming the oxide semiconductor film 111 are in contact with the oxide semiconductor film 111, an interface state is not easily formed at the interfaces between the oxide semiconductor film 107 and the oxide semiconductor film 111 and between the oxide semiconductor film 115 and the oxide semiconductor film 111.

The oxide semiconductor films 107 and 115 function as barrier films that prevent constituent elements of the gate insulating films 105 and 117 from entering the oxide semiconductor film 111 and forming an impurity state.

For example, in the case of using a silicon-containing insulating film as the gate insulating films 105 and 117, silicon in the gate insulating films 105 and 117 or carbon which might be contained in the gate insulating films 105 and 117 enters the oxide semiconductor film 107 or the oxide semiconductor film 115 to a depth of several nanometers from the interface in some cases. An impurity such as silicon or carbon entering the oxide semiconductor film forms an impurity state. The impurity state serves as a donor to generate an electrons; thus, an n-type semiconductor might be formed.

However, when the thicknesses of the oxide semiconductor film 107 and the oxide semiconductor film 115 are each larger than several nanometers, the impurity such as silicon or carbon does not reach the oxide semiconductor film 111, so that the influence of impurity state is suppressed.

Thus, providing the oxide semiconductor films 107 and 115 makes it possible to reduce variations in electrical characteristics of the transistor, such as threshold voltage.

In the case where a channel is formed at interfaces between the gate insulating film 105 and the oxide semiconductor film 111 and between the gate insulating film 117 and the oxide semiconductor film 111, interface scattering occurs at the interfaces and the field-effect mobility of the transistor is decreased. However, since the oxide semiconductor film 107 and 115 containing one or more kinds of metal elements forming the oxide semiconductor film 111 are provided in contact with the oxide semiconductor film 111, scattering of carriers does not easily occur at the interfaces between the oxide semiconductor film 111 and each of the oxide semiconductor films 107 and 115, and thus the field-effect mobility of the transistor can be increased.

In this embodiment, the number of oxygen vacancies in the oxide semiconductor film 111, and further the number of oxygen vacancies in the oxide semiconductor films 107 and 115 in contact with the oxide semiconductor film 111 can be reduced; thus, the density of localized states of the oxide semiconductor film 111 can be reduced. As a result, the transistor 100 in this embodiment has small variations in threshold voltage and high reliability. Further, the transistor 100 of this embodiment has excellent electric characteristics.

The pair of electrodes 113 a and 113 b is formed to have a single-layer structure or a stacked-layer structure including, as a conductive material, any of metals such as aluminum, titanium, chromium, nickel, copper, yttrium, zirconium, molybdenum, silver, tantalum, manganese, and tungsten or an alloy containing any of these metals as a main component. For example, a single-layer structure of an aluminum film containing silicon, a single-layer structure of a copper film containing manganese, a two-layer structure in which a titanium film is stacked over an aluminum film, a two-layer structure in which a titanium film is stacked over a tungsten film, a two-layer structure in which a copper film is stacked over a copper-magnesium alloy film, a two-layer structure in which a copper film is stacked over a copper-magnesium-aluminum alloy film, a three-layer structure in which a titanium film or a titanium nitride film, an aluminum film or a copper film, and a titanium film or a titanium nitride film are stacked in this order, a three-layer structure in which a molybdenum film or a molybdenum nitride film, an aluminum film or a copper film, and a molybdenum film or a molybdenum nitride film are stacked in this order, a three-layer structure in which a copper-magnesium alloy film, a copper film, and a copper-magnesium alloy film are stacked in this order, and the like can be given. Note that a transparent conductive material containing indium oxide, tin oxide, or zinc oxide may be used.

Note that in the oxide semiconductor film 111, a channel formation region refers to a region which overlaps with the gate electrode 119 and is positioned between the pair of electrodes 113 a and 113 b. Further, a channel region refers to a region through which carriers mainly flow in the channel formation region. Here, a channel region is part of the oxide semiconductor film 111, which is positioned between the pair of electrodes 113 a and 113 b. A channel length refers to the distance between the pair of electrodes 113 a and 113 b.

As for the pair of electrodes 113 a and 113 b, it is preferable to use a conductive material which is easily bonded to oxygen, such as tungsten, titanium, aluminum, copper, molybdenum, chromium, or tantalum, or an alloy thereof. Tungsten or titanium with a relatively high melting point is preferably used, which allows subsequent process temperatures to be relatively high. Note that the conductive material which is easily bonded to oxygen includes a material to which oxygen is easily diffused. In this case, oxygen in the oxide semiconductor film 111 and the conductive material contained in the pair of electrodes 113 a and 113 b are bonded, and accordingly, an oxygen vacancy region is formed in the oxide semiconductor film 111. Further, in some cases, part of constituent elements of the conductive material forming the pair of electrodes 113 a and 113 b is mixed into the oxide semiconductor film 111. In this case, n-type regions (low resistance regions) are formed in regions in contact with the pair of electrodes 113 a and 113 b at least in the oxide semiconductor film 111. The n-type regions (low resistance regions) function as a source region and a drain region.

A region having high oxygen concentration may be formed in part of the pair of electrodes 113 a and 113 b in contact with the low-resistance regions. Constituent elements of the oxide semiconductor film 111 enter the pair of electrodes 113 a and 113 b in contact with the low-resistance regions in some cases. In other words, in the vicinities of the interfaces between the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b, regions which can be called mixed regions or mixed layers of the two contacting layers are formed in some cases.

Since the n-type regions (low-resistance regions) have high conductivity, contact resistance between the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b can be reduced, and thus, the on-state current of the transistor can be increased.

The gate insulating film 117 can be formed using any of the materials that can be used as the material of the gate insulating film 105 as appropriate.

The gate electrode 119 can be formed using any of the materials that can be used as the material of the gate electrode 103 as appropriate.

The insulating films 121 and 123 can be formed using any of the materials and formation methods which can be used as those of the gate insulating film 117, as appropriate. Although a stacked-layer structure of the insulating films 121 and 123 is used here, a single-layer structure may be used as well.

As the insulating film 121 or the insulating film 123, an aluminum oxide film is preferably used. Since aluminum oxide functions as a barrier film against hydrogen, water, and oxygen, when using an aluminum oxide film as the insulating film 121 or 123, release of oxygen contained in the oxide semiconductor film 111 and diffusion of water, hydrogen, and the like from the outside to the oxide semiconductor film 111 can be prevented.

In the case where the insulating film 121 and the insulating film 123 are oxide insulating films, an oxide insulating film containing oxygen in excess of the stoichiometric composition may be used as one or both of the insulating film 121 and the insulating film 123. In this way, the oxygen in the insulating film is transferred to the oxide semiconductor film, so that oxygen vacancies can be reduced.

As the oxide insulating film containing oxygen in excess of the stoichiometric composition, it is preferable to use an oxide insulating film from which oxygen molecules at more than or equal to 1.0×10¹⁸ molecules/cm³ are released in thermal desorption spectroscopy (hereinafter referred to as TDS) at a surface temperature of the oxide insulating film of higher than or equal to 100° C. and lower than or equal to 700° C., or higher than or equal to 100° C. and lower than or equal to 500° C.

The oxide insulating film containing oxygen in excess of the stoichiometric composition has such a thickness as to allow oxygen to be supplied to the oxide semiconductor film 111. For example, the thickness can be more than or equal to 50 nm and less than or equal to 500 nm, or more than or equal to 50 nm and less than or equal to 400 nm.

As one or both of the insulating film 121 and the insulating film 123, a nitride insulating film where the hydrogen content is low may be provided. The nitride insulating film is preferably as follows, for example: the number of hydrogen molecules released from the nitride insulating film is less than 5.0×10²¹ molecules/cm³, preferably less than 3.0×10²¹ molecules/cm³, and further preferably less than 1.0×10²¹ molecules/cm³ when measured by TDS in which heat treatment is performed at a film surface temperature of higher than or equal to 100° C. and lower or equal to 700° C., preferably higher than or equal to 100° C. and lower than or equal to 500° C.

The nitride insulating film has such a thickness as to allow prevention of impurities such as hydrogen and water from the outside. For example, the thickness can be more than or equal to 50 nm and less than or equal to 200 nm, preferably more than or equal to 50 nm and less than or equal to 150 nm, and further preferably more than or equal to 50 nm and less than or equal to 100 nm.

<Manufacturing Method of Semiconductor Device>

A method for manufacturing a semiconductor device is described with reference to FIGS. 2A to 2D and FIGS. 3A to 3C.

Films of the transistor (e.g., an insulating film, an oxide semiconductor film, a metal oxide film, and a conductive film) can be formed by a sputtering method, a chemical vapor deposition (CVD) method, a vacuum vapor deposition method, or a pulsed laser deposition (PLD) method. Alternatively, a coating method or a printing method can be used. Although the sputtering method and a plasma-enhanced chemical vapor deposition (PECVD) method are typical examples of the film formation method, a thermal CVD method may be used as well. As a thermal CVD method, a metal organic chemical vapor deposition (MOCVD) method or an atomic layer deposition (ALD) method may be used, for example.

Deposition by a thermal CVD method may be performed in such a manner that the pressure in a chamber is set to an atmospheric pressure or a reduced pressure, and a source gas and an oxidizer are supplied to the chamber at a time and react with each other in the vicinity of the substrate or over the substrate. Thus, no plasma is generated in the deposition; therefore, the thermal CVD method has an advantage that no defect due to plasma damage is caused.

Deposition by an ALD method may be performed in such a manner that the pressure in a chamber is set to an atmospheric pressure or a reduced pressure, source gases for reaction are sequentially introduced into the chamber, and then the sequence of the gas introduction is repeated. For example, two or more kinds of source gases are sequentially supplied to the chamber by switching respective switching valves (also referred to as high-speed valves). In such a case, a first source gas is introduced, an inert gas (e.g., argon or nitrogen) or the like is introduced at the same time or after the first source gas is introduced so that the source gases are not mixed, and then a second source gas is introduced. Note that in the case where the first source gas and the inert gas are introduced at a time, the inert gas serves as a carrier gas, and the inert gas may also be introduced at the same time as the introduction of the second source gas. Alternatively, the first source gas may be exhausted by vacuum evacuation instead of the introduction of the inert gas, and then the second source gas may be introduced. The first source gas is adsorbed on the surface of the substrate to form a first layer; then the second source gas is introduced to react with the first layer; as a result, a second layer is stacked over the first layer, so that a thin film is formed.

The sequence of the gas introduction is repeated a plurality of times until a desired thickness is obtained, whereby a thin film with excellent step coverage can be formed. The thickness of the thin film can be adjusted by the number of repetition times of the gas introduction sequence; therefore, an ALD method makes it possible to accurately adjust the thickness and thus is suitable for manufacturing a minute FET.

As illustrated in FIG. 2A, the gate electrode 103 is formed over the substrate 101, an insulating film 104 is formed over the substrate 101 and the gate electrode 103, and then an oxide semiconductor film 106 is formed over the insulating film 104. Next, oxygen 108 is added to the oxide semiconductor film 106.

Note that the insulating film 104 is processed into the gate insulating film 105 later. The oxide semiconductor film 106 is processed into the oxide semiconductor film 107 later.

A method for forming the gate electrode 103 will be described below. First, a conductive film is formed by a sputtering method, a chemical vapor deposition (CVD) method such as a metal organic chemical vapor deposition (MOCVD) method, a metal chemical vapor deposition method, an atomic layer deposition (ALD) method, or a plasma-enhanced chemical vapor deposition (PECVD) method, an evaporation method, a pulsed laser deposition (PLD) method, or the like. Then, a mask is formed over the conductive film by a lithography process. Then, part of the conductive film is etched using the mask to form the gate electrode 103. Then, the mask is removed.

For example, a tungsten film can be formed as the conductive film with a deposition apparatus employing an ALD method. In that case, a WF₆ gas and a B₂H₆ gas are sequentially introduced more than once to form an initial tungsten film, and then a WF₆ gas and an H₂ gas are introduced at a time, so that a tungsten film is formed. Note that an SiH₄ gas may be used instead of a B₂H₆ gas.

Here, a 20-nm-thick tungsten film is formed as the conductive film by a sputtering method. Then, a mask is formed over the conductive film by a lithography step, and the conductive film is wet-etched using the mask, so that the gate electrode 103 is formed.

The insulating film 104 can be formed by a sputtering method, a chemical vapor deposition (CVD) method such as a metal organic chemical vapor deposition (MOCVD) method, an atomic layer deposition (ALD) method, or a plasma-enhanced chemical vapor deposition (PECVD) method, a pulsed laser deposition (PLD) method, a coating method, a printing method, or the like.

In the case where the insulating film 104 is formed using a silicon oxide film or a silicon oxynitride film, a deposition gas containing silicon and an oxidizing gas are preferably used as a source gas. Typical examples of the deposition gas containing silicon include silane, disilane, trisilane, and silane fluoride. As the oxidizing gas, oxygen, ozone, dinitrogen monoxide, and nitrogen dioxide can be given as examples.

In the case where a gallium oxide film is formed as the insulating film 104, an MOCVD method can be employed.

In the case where a hafnium oxide film is formed as the insulating film 104 by a thermal CVD method such as an MOCVD method or an ALD method, two kinds of gases, i.e., ozone (O₃) as an oxidizer and a source material gas which is obtained by vaporizing a liquid containing a solvent and a hafnium precursor compound (a hafnium alkoxide solution, which is typified by tetrakis(dimethylamide)hafnium (TDMAH)), are used. Note that the chemical formula of tetrakis(dimethylamide)hafnium is Hf[N(CH₃)₂]₄. Examples of another material liquid include tetrakis(ethylmethylamide)hafnium.

In the case where an aluminum oxide film is formed as the insulating film 104 by a thermal CVD method such as an MOCVD method or an ALD method, two kinds of gases, i.e., H₂O as an oxidizer and a source material gas which is obtained by vaporizing a liquid containing a solvent and an aluminum precursor compound (e.g., trimethylaluminum (TMA)) are used. Note that the chemical formula of trimethylaluminum is Al(CH₃)₃. Examples of another material liquid include tris(dimethylamide)aluminum, triisobutylaluminum, and aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate).

In the case where a silicon oxide film is formed as the insulating film 104 by a thermal CVD method such as an MOCVD method or an ALD method, hexachlorodisilane is adsorbed on a deposition surface, chlorine contained in adsorbate is removed, and radicals of an oxidizing gas (e.g., O₂ or dinitrogen monoxide) are supplied to react with the adsorbate.

Here, as the insulating film 104, a 100-nm-thick silicon oxynitride film is formed by a CVD method.

Then, heat treatment may be performed to release water, hydrogen, or the like contained in the insulating film 104. As a result, the concentration of water, hydrogen, or the like contained in the gate insulating film 105 that is to be formed later can be reduced. The heat treatment can reduce the amount of water, hydrogen, or the like diffused into the oxide semiconductor film 111.

The oxide semiconductor film 106 can be formed by a sputtering method, a coating method, a pulsed laser deposition method, a laser ablation method, a metal organic chemical vapor deposition (MOCVD) method, an atomic layer deposition (ALD) method, or the like.

In the case where the oxide semiconductor film 106 is formed by a sputtering method, a power supply device for generating plasma can be an RF power supply device, an AC power supply device, a DC power supply device, or the like as appropriate.

As a sputtering gas, a rare gas (typically argon), an oxygen gas, or a mixed gas of a rare gas and oxygen is used as appropriate. In the case of using the mixed gas of a rare gas and oxygen, the proportion of oxygen to a rare gas is preferably increased.

Further, a target may be appropriately selected in accordance with the composition of the oxide semiconductor film 106 to be formed.

For example, in the case where the oxide semiconductor film is formed by a sputtering method at a substrate temperature higher than or equal to 150° C. and lower than or equal to 750° C., preferably higher than or equal to 150° C. and lower than or equal to 450° C., further preferably higher than or equal to 200° C. and lower than or equal to 350° C., the oxide semiconductor film can be a CAAC-OS film.

For the deposition of the CAAC-OS film, the following conditions are preferably used.

By inhibiting entry of impurities during the deposition, the crystal state can be prevented from being broken by the impurities. For example, the concentration of impurities (e.g., hydrogen, water, carbon dioxide, or nitrogen) that exist in a deposition chamber may be reduced. Furthermore, the concentration of impurities in a deposition gas may be reduced. Specifically, a deposition gas whose dew point is −80° C. or lower, preferably −100° C. or lower is used.

For example, in the case where an oxide semiconductor film, e.g., an In—Ga—Zn—O film is formed using a deposition apparatus employing an ALD method, an In(CH₃)₃ gas and an O₃ gas are sequentially introduced a plurality of times to form an In—O layer, a Ga(CH₃)₃ gas and an O₃ gas are introduced at a time to form a Ga—O layer, and then a Zn(CH₃)₂ gas and an O₃ gas are introduced at a time to form a Zn—O layer. Note that the order of these layers is not limited to this example. A mixed compound layer such as an In—Ga—O layer, an In—Zn—O layer, or a Ga—Zn—O layer may be formed by mixing these gases. Note that although an H₂O gas which is obtained by bubbling with an inert gas such as Ar may be used instead of an O₃ gas, it is preferable to use an O₃ gas that does not contain H. Instead of an In(CH₃)₃ gas, an In(C₂H₅)₃ gas may be used. Instead of a Ga(CH₃)₃ gas, a Ga(C₂H₅)₃ gas may be used. Furthermore, a Zn(CH₃)₂ gas may be used.

Here, as the oxide semiconductor film 106, a 10-nm-thick In—Ga—Zn oxide film (In:Ga:Zn=1:3:2) is formed by a sputtering method.

The oxygen 108 added to the oxide semiconductor film 106 is at least one kind selected from oxygen radicals, oxygen atoms, oxygen atomic ions, oxygen molecular ions, and the like. As a method for adding the oxygen 108 to the oxide semiconductor film 106, an ion doping method, an ion implantation method, and the like can be given.

In the case of using an ion implantation method as the method for adding the oxygen 108, damage to the oxide semiconductor film 106 can be reduced by using oxygen molecular ions as the oxygen 108 added to the oxide semiconductor film 106. Oxygen molecular ions are broken down into oxygen atomic ions at the surface of the oxide semiconductor film 106, and the oxygen atomic ions are added to the oxide semiconductor film 106. Since energy for breaking oxygen molecules down into oxygen atoms is used, the energy per oxygen atomic ion in the case of adding oxygen molecular ions to the oxide semiconductor film 106 is lower than that in the case of adding oxygen atomic ions to the oxide semiconductor film 106. Therefore, in the case of adding oxygen molecular ions to the oxide semiconductor film 106, damage to the oxide semiconductor film 106 can be reduced.

By using oxygen molecular ions, the energy of each oxygen atomic ion injected to the insulating film 104 is lowered, which makes the injected oxygen atomic ion be positioned in a shallow region. Accordingly, oxygen atoms easily move by later heat treatment, so that more oxygen can be supplied to the oxide semiconductor film 109 that is to be formed later.

In the case of injecting oxygen molecular ions, the energy per oxygen atomic ion is low as compared with the case of injecting oxygen atomic ions. Thus, by using oxygen molecular ions for injection, the acceleration voltage can be increased and throughput can be increased. Moreover, by using oxygen molecular ions for injection, the dose can be half of the amount that is necessary in the case of using oxygen atomic ions. As a result, throughput can be increased.

In the case of adding oxygen to the oxide semiconductor film 106, it is preferable that oxygen be added to the oxide semiconductor film 106 so that a peak of the concentration profile of oxygen atomic ions can be positioned in the oxide semiconductor film 106. As a result, damage to the gate insulating film 105 that is to be formed later can be reduced. In other words, defects in the gate insulating film 105 can be reduced, so that variations in electrical characteristics of the transistor can be reduced. Furthermore, in the case where oxygen is added to the oxide semiconductor film 106 so that the amount of added oxygen atoms at the interface between the insulating film 104 and the oxide semiconductor film 106 is less than 1×10²¹ atoms/cm³, less than 1×10²⁰ atoms/cm³, or less than 1×10¹⁹ atoms/cm³, the amount of oxygen added to the gate insulating film 105 that is to be formed later can be reduced. As a result, damage to the gate insulating film 105 that is to be formed later can be reduced, whereby variations in electrical characteristics of the transistor can be prevented.

Plasma treatment in which the oxide semiconductor film 106 is exposed to plasma generated in an atmosphere containing oxygen may be performed, to add oxygen to the oxide semiconductor film 106. As the atmosphere containing oxygen, an atmosphere containing an oxidation gas such as oxygen, ozone, dinitrogen monoxide, or nitrogen dioxide can be given. Note that it is preferable that the oxide semiconductor film 106 be exposed to plasma generated in a state where bias is applied on the substrate 101 side, because the amount of oxygen added to the oxide semiconductor film 106 can be increased. As an example of an apparatus used in such plasma treatment, an ashing apparatus is given.

Here, oxygen molecular ions are added to the oxide semiconductor film 106 by an ion implantation method with a dose of 1×10¹⁶/cm² at an acceleration voltage of 5 keV.

Through the above-described steps, an oxide semiconductor film 106 a to which oxygen is added as illustrated in FIG. 2B can be formed. As a result, the number of oxygen vacancies in the oxide semiconductor film 109 can be reduced by heat treatment in a later step. Note that the oxide semiconductor film 106 a to which oxygen is added has a low film density compared with the oxide semiconductor film 106 to which oxygen is not added.

Next, as illustrated in FIG. 2B, the oxide semiconductor film 109 is formed over the oxide semiconductor film 106 a to which oxygen is added.

The oxide semiconductor film 109 can be formed by a sputtering method, a coating method, a pulsed laser deposition method, a laser ablation method, a metal organic chemical vapor deposition (MOCVD) method, an atomic layer deposition (ALD) method, or the like.

As a power supply device for generating plasma in the case of forming the oxide semiconductor film 109, an RF power supply device, an AC power supply device, a DC power supply device, or the like can be used as appropriate.

As a sputtering gas, a rare gas (typically argon), an oxygen gas, or a mixed gas of a rare gas and oxygen is used as appropriate. In the case of using the mixed gas of a rare gas and oxygen, the proportion of oxygen to a rare gas is preferably increased.

Further, a target may be appropriately selected in accordance with the composition of the oxide semiconductor film 109.

Note that in the case where the oxide semiconductor film 109 is formed by, for example, a sputtering method, the substrate temperature may be set to higher than or equal to 100° C. and lower than or equal to 450° C., preferably higher than or equal to 170° C. and lower than or equal to 350° C., and the oxide semiconductor film 109 may be formed while being heated.

Here, as the oxide semiconductor film 109, a 30-nm-thick In—Ga—Zn oxide film (In:Ga:Zn=1:1:1) is formed by a sputtering method.

Next, heat treatment is performed so that part of oxygen contained in the oxide semiconductor film 106 a to which oxygen is added can be transferred to the oxide semiconductor film 109; consequently, oxygen vacancies in the oxide semiconductor film 109 can be reduced. This oxide semiconductor film with reduced oxygen vacancies is represented as the oxide semiconductor film 109 a in FIG. 2C. Oxygen vacancies in the oxide semiconductor film 106 a to which oxygen is added can be reduced. This oxide semiconductor film is represented as the oxide semiconductor film 106 b in FIG. 2C. Hydrogen, water, and the like contained in the oxide semiconductor film 106 a to which oxygen is added and the oxide semiconductor film 109 can be released. As a result, the amount of impurities contained in the oxide semiconductor film 106 a to which oxygen is added and the oxide semiconductor film 109 can be reduced.

The temperature of heat treatment is preferably within the range of temperatures at which oxygen is transferred from the oxide semiconductor film 106 a to which oxygen is added to the oxide semiconductor film 109. The temperature is typically higher than or equal to 250° C. and lower than the strain point of the substrate, preferably higher than or equal to 300° C. and lower than or equal to 550° C., further preferably higher than or equal to 350° C. and lower than or equal to 510° C.

The heat treatment is performed in an inert gas atmosphere containing nitrogen or a rare gas such as helium, neon, argon, xenon, or krypton. Further, after heat treatment performed in an inert gas atmosphere, heat treatment may be additionally performed in an oxygen atmosphere or a dry air atmosphere (air whose dew point is lower than or equal to −80° C., preferably lower than or equal to −100° C., further preferably lower than or equal to −120° C.). Note that it is preferable that hydrogen, water, and the like be not contained in an inert gas and oxygen, like the dry air, and the dew point is preferably lower than or equal to −80° C., further preferably lower than or equal to −100° C. The treatment time is 3 minutes to 24 hours.

In the heat treatment, instead of an electric furnace, any device for heating an object by heat conduction or heat radiation from a heating element such as a resistance heating element may be used. For example, a rapid thermal anneal (RTA) apparatus such as a gas rapid thermal anneal (GRTA) apparatus or a lamp rapid thermal anneal (LRTA) apparatus can be used. An LRTA apparatus is an apparatus for heating an object by radiation of light (an electromagnetic wave) emitted from a lamp such as a halogen lamp, a metal halide lamp, a xenon arc lamp, a carbon arc lamp, a high pressure sodium lamp, or a high pressure mercury lamp. A GRTA apparatus is an apparatus for heat treatment using a high-temperature gas. As the high-temperature gas, an inert gas such as nitrogen or a rare gas like argon is used.

Here, after heat treatment is performed at 450° C. for 1 hour in a nitrogen atmosphere, heat treatment is performed at 450° C. for 1 hour in an oxygen atmosphere.

Through the above-described steps, oxygen vacancies in the oxide semiconductor films can be reduced. The oxide semiconductor films can have low density of localized states.

Note that the heat treatment may be performed in a later step, not this step. In other words, in another heating step performed later, part of oxygen contained in the oxide semiconductor film 106 a to which oxygen is added may be transferred to the oxide semiconductor film 109. As a result, the number of heating steps can be reduced.

Then, after a mask is formed over the oxide semiconductor film 109 a by a lithography process, part of the oxide semiconductor film 106 b and part of the oxide semiconductor film 109 a are each etched using the mask. Accordingly, the oxide semiconductor film 107 and an oxide semiconductor film 110 are formed as illustrated in FIG. 2D. Then, the mask is removed. Note that in the etching step, it is preferable that part of the insulating film 104 be etched. As a result, a transistor with the s-channel structure where, in the channel width direction, the side surfaces of the oxide semiconductor film 107 and the oxide semiconductor film 111 face the gate electrode 119 with the gate insulating film interposed therebetween can be formed. Here, the insulating film 104 which is partly etched is referred to as the gate insulating film 105.

Here, a mask is formed over the oxide semiconductor film 109 a by a lithography process, and the oxide semiconductor film 106 b and the oxide semiconductor film 109 a are wet-etched using the mask, so that the oxide semiconductor film 107 and the oxide semiconductor film 110 are formed.

Next, the pair of electrodes 113 a and 113 b is formed over the oxide semiconductor film 110.

A method for forming the pair of electrodes 113 a and 113 b is described below. A conductive film is formed by a sputtering method, a chemical vapor deposition (CVD) method such as a metal organic chemical vapor deposition (MOCVD) method, a metal chemical vapor deposition method, an atomic layer deposition (ALD) method, or a plasma-enhanced chemical vapor deposition (PECVD) method, an evaporation method, a pulsed laser deposition (PLD) method, or the like. Then, a mask is formed over the conductive film by a lithography process. Then, part of the conductive film is etched using the mask to form the pair of electrodes 113 a and 113 b. Then, the mask is removed.

Note that in the case where a transistor having an extremely short channel length is formed, at least the conductive film in a region to divide the pair of electrodes 113 a and 113 b is etched using a resist mask that is processed by a method suitable for micropatterning, such as electron beam exposure, liquid immersion exposure, or EUV exposure. Note that by the use of a positive type resist for the resist mask, the exposed region can be minimized and throughput can be improved. In the above-described manner, a transistor having a channel length of 100 nm or less, further, 30 nm or less can be formed. Alternatively, minute processing may be performed by an exposure technology which uses light with an extremely short wavelength (e.g., extreme ultraviolet (EUV)), X-rays, or the like.

Here, a 10 nm-thick tungsten film is formed as the conductive film by a sputtering method. Then, a mask is formed over the conductive film by a lithography process and the conductive film is dry-etched with use of the mask to form the pair of electrodes 113 a and 113 b.

After the pair of electrodes 113 a and 113 b is formed, cleaning treatment is preferably performed to remove an etching residue. A short circuit of the pair of electrodes 113 a and 113 b can be suppressed by this cleaning treatment. The cleaning treatment can be performed using an alkaline solution such as a tetramethylammonium hydroxide (TMAH) solution, an acidic solution such as diluted hydrofluoric acid, an oxalic acid solution, or a phosphoric acid solution. By the cleaning treatment, part of the oxide semiconductor film 110 is etched, so that the oxide semiconductor film 111 having a depression is formed (see FIG. 3A).

Next, as illustrated in FIG. 3B, the oxide semiconductor film 115 is formed over the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b, the gate insulating film 117 is formed over the oxide semiconductor film 115, and the gate electrode 119 is formed over the gate insulating film 117.

A method for forming the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119 is described below. First, an oxide semiconductor film is formed using any of the methods that can be used for forming the oxide semiconductor film 106 as appropriate. Next, an insulating film is formed using any of the methods that can be used for forming an insulating film 116. Then, a conductive film is formed. Then, a mask is formed over the conductive film by a lithography process. Next, the oxide semiconductor film, the insulating film, and the conductive film are etched using the mask to form the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119. After that, the mask is removed.

Here, as the oxide semiconductor film, a 5-nm-thick In—Ga—Zn oxide film (In:Ga:Zn=1:3:2) is formed by a sputtering method. Next, as the insulating film, a 10-nm-thick silicon oxynitride film is formed by a CVD method. Then, as the conductive film, a 20-nm-thick tungsten film is formed by a sputtering method. Then, a mask is formed over the conductive film by a lithography process. Next, the oxide semiconductor film, the insulating film, and the conductive film are etched using the mask to form the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119. After that, the mask is removed.

In the transistor 100, by providing the oxide semiconductor film 115 in which oxygen vacancies are unlikely to occur, release of oxygen from side surfaces of the oxide semiconductor film 111 in the channel width direction is suppressed, so that generation of oxygen vacancies can be suppressed. As a result, a transistor which has improved electrical characteristics and high reliability can be provided.

As illustrated in FIG. 3C, the insulating film 121 and the insulating film 123 are formed sequentially over the gate insulating film 105, the pair of electrodes 113 a and 113 b, the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119. After that, heat treatment is preferably performed.

The insulating film 121 and the insulating film 123 can be formed by a sputtering method, a CVD method, or the like as appropriate.

In the case where the insulating film 121 and the insulating film 123 are oxide insulating films containing oxygen in excess of the stoichiometric composition, the oxide insulating films containing oxygen in excess of the stoichiometric composition can formed by a CVD method, a sputtering method, or the like. After the oxide insulating films are formed by a CVD method, a sputtering method, or the like, oxygen may be added to the oxide insulating films by an ion implantation method, an ion doping method, plasma treatment, or the like.

The heat treatment is performed typically at a temperature higher than or equal to 150° C. and lower than the strain point of the substrate, preferably higher than or equal to 250° C. and lower than or equal to 500° C., further preferably higher than or equal to 300° C. and lower than or equal to 450° C.

Here, a 40-nm-thick aluminum oxide film is formed as the insulating film 121 by a sputtering method, and a 150-nm-thick silicon oxynitride film is formed as the insulating film 123 by a CVD method. Further, heat treatment is performed at 350° C. in an oxygen atmosphere for 1 hour.

Through the above-described steps, the density of localized states of the oxide semiconductor films is lowered, and thus a transistor with excellent electrical characteristics can be manufactured. In addition, a highly reliable transistor with few variations with time in electrical characteristics or few variations in electrical characteristics due to a stress test can be manufactured.

<Band Structure>

Here, a band structure is described. For easy understanding, the band structure is illustrated with the energy levels (Ec) at the conduction band minimum of the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 111, the oxide semiconductor film 115, and the gate insulating film 117.

As illustrated in FIGS. 4A and 4B, the energy at the conduction band minimum changes continuously within the oxide semiconductor films 107, 111, and 115. This can be understood also from the fact that the constituent elements are common among the oxide semiconductor films 107, 111, and 115 and oxygen is easily diffused among the oxide semiconductor films 107, 111, and 115. Thus, the oxide semiconductor films 107, 111, and 115 have a continuous physical property although they are a stack of films having different compositions.

The oxide semiconductor films, which contain the same main components and are stacked, are not simply stacked but formed to have continuous junction (here, particularly a U-shaped (U shape) well structure where the energy at the conduction band minimum is continuously changed between the films). In other words, a stacked-layer structure is formed such that there exist no impurities which form a defect level such as a trap center or a recombination center at each interface. If impurities are mixed between the films in the stacked multilayer film, the continuity of the energy band is lost and carriers disappear by a trap or recombination at the interface.

Note that FIG. 4A illustrates the case where the energy level (Ec) at the conduction band minimum of the oxide semiconductor film 107 and that of the oxide semiconductor film 115 are equal to each other; however, they may be different from each other. For example, FIG. 4B illustrates part of the band structure in the case where the energy level (Ec) at the conduction band minimum of the oxide semiconductor film 115 is closer to the vacuum level than that of the oxide semiconductor film 107 is.

As illustrated in FIGS. 4A and 4B, the oxide semiconductor film 111 serves as a well and a channel of the transistor 100 is formed in the oxide semiconductor film 111. Note that a channel having a U-shaped well structure in which the energy at the conduction band minimum continuously changes like the one formed in the oxide semiconductor films 107, 111, and 115, can also be referred to as a buried channel.

Note that trap levels due to impurities or defects might be formed in the vicinity of the interface between an insulating film such as a silicon oxide film and each of the oxide semiconductor films 107 and 115. The oxide semiconductor film 111 can be distanced away from the trap levels owing to the existence of the oxide semiconductor films 107 and 115. However, when the energy difference between the Ec of the oxide semiconductor film 107 or 115 and the Ec of the oxide semiconductor film 111 is small, electrons in the oxide semiconductor film 111 might reach the trap levels across the energy difference. When the electrons are trapped in the trap levels, negative fixed charges are generated at the interface with the insulating film, whereby the threshold voltage of the transistor is shifted in the positive direction.

Thus, to reduce a change in the threshold voltage of the transistor, an energy difference between the Ec of the oxide semiconductor film 111 and the Ec of each of the oxide semiconductor films 107 and 115 is necessary. The energy difference is preferably greater than or equal to 0.1 eV, further preferably greater than or equal to 0.2 eV.

The oxide semiconductor films 107, 111, and 115 preferably include a crystal. In particular, when a crystal in which c-axes are aligned is used, the transistor can have stable electrical characteristics.

In the band structure illustrated in FIG. 4B, instead of the oxide semiconductor film 115, an In—Ga oxide (e.g., an In—Ga oxide with an atomic ratio of In:Ga=7:93) may be provided between the oxide semiconductor film 111 and the gate insulating film 117.

Since the transistor described in this embodiment includes the oxide semiconductor films 107 and 115 that each include one or more kinds of metal elements included in the oxide semiconductor film 111, interface states can be reduced at the interface between the oxide semiconductor film 107 and the oxide semiconductor film 111 and the interface between the oxide semiconductor film 115 and the oxide semiconductor film 111. Thus, providing the oxide semiconductor films 107 and 115 makes it possible to reduce variations or changes in electrical characteristics of the transistor, such as threshold voltage.

When a channel is formed at the interface between the gate insulating film 117 and the oxide semiconductor film 111, interface scattering occurs at the interface and the field-effect mobility of the transistor may decrease in some cases. In the transistor of this structure, however, the oxide semiconductor film 115 includes one or more kinds of metal elements included in the semiconductor film 111. Therefore, scattering of carriers is unlikely to occur at the interface between the semiconductor film 111 and the oxide semiconductor film 115, and thus the field-effect mobility of the transistor can be increased.

<Variation 1>

Transistors having different shapes of the oxide semiconductor film 115 and the gate insulating film 117 from those of the transistor 100 illustrated in FIGS. 1A to 1C will be described with reference to FIGS. 5A to 5C.

A transistor 100 a illustrated in FIG. 5A includes an oxide semiconductor film 115 a that is in contact with the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b, and a gate insulating film 117 a that is in contact with the oxide semiconductor film 115 a. The gate insulating film 117 a is in contact with the gate electrode 119.

In the transistor 100 a, end portions of the oxide semiconductor film 115 a and the gate insulating film 117 a are located on the outer side of an end portion of the gate electrode 119.

A transistor 100 b illustrated in FIG. 5B includes an oxide semiconductor film 115 b that is in contact with the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b, and a gate insulating film 117 b that is in contact with the oxide semiconductor film 115 b. The gate insulating film 117 b is in contact with the gate electrode 119.

In the transistor 100 b, the oxide semiconductor film 115 b and the gate insulating film 117 b are each not disconnected and cover the pair of electrodes 113 a and 113 b and the gate insulating film 105.

A transistor 100 c illustrated in FIG. 5C includes an oxide semiconductor film 115 c that is in contact with the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b, and a gate insulating film 117 b that is in contact with the oxide semiconductor film 115 c. The gate insulating film 117 b is in contact with the gate electrode 119.

In the transistor 100 c, an end portion of the oxide semiconductor film 115 c is located on the outer side of an end portion of the gate electrode 119, and the gate insulating film 117 b is not disconnected and covers the pair of electrodes 113 a and 113 b and the gate insulating film 105.

The oxide semiconductor films 115 a, 115 b, and 115 c can be formed using the same material as that of the oxide semiconductor film 115, as appropriate. The gate insulating films 117 a and 117 b can be formed using the same material as that of the gate insulating film 117, as appropriate.

Here, manufacturing methods of the transistors 100 a, 100 b, and 100C will be described.

First, the manufacturing method of the transistor 100 a will be described. Through the steps of FIGS. 2A to 2D and FIG. 3A, the gate electrode 103, the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 111, and the pair of electrodes 113 a and 113 b are formed over the substrate 101.

Then, an oxide semiconductor film to be the oxide semiconductor film 115 a is formed over the gate insulating film 105, the oxide semiconductor film 111, and the pair of electrodes 113 a and 113 b. Further, an insulating film to be the gate insulating film 117 a is formed over the oxide semiconductor film to be the oxide semiconductor film 115 a. Next, a conductive film is formed over the insulating film to be the gate insulating film 117 a. Further, a mask is formed over the conductive film by a lithography process, and etched using the mask to form the gate electrode 119. Then, the mask is removed.

In the etching step, since the pair of electrodes 113 a and 113 b is covered with the insulating film to be the gate insulating film 117 a, surfaces of the pair of electrodes 113 a and 113 b can be prevented from bearing electrical charges. Consequently, electrostatic destruction between the gate electrode 119 and the pair of electrodes 113 a and 113 b is unlikely to occur and yield can be increased.

Next, a mask is formed over the gate electrode 119 and the insulating film to be the gate insulating film 117 a by a lithography process, and the oxide semiconductor film to be the oxide semiconductor film 115 a and the insulating film to be the gate insulating film 117 a are etched using the mask, to form the oxide semiconductor film 115 a and the gate insulating film 117 a.

In the etching step, since the gate electrode 119 is covered with the mask, a surface of the gate electrode 119 can be prevented from bearing electrical charges. Consequently, electrostatic destruction between the gate electrode 119 and the pair of electrodes 113 a and 113 b is unlikely to occur although the pair of electrodes 113 a and 113 b is exposed at the time of forming the oxide semiconductor film 115 a and the gate insulating film 117 a; thus, yield can be increased.

The later steps are the same as those for the transistor 100 of Embodiment 1. Through the later steps, the transistor 100 a can be manufactured.

The manufacturing method of the transistor 100 b will be described. Through the steps of FIGS. 2A to 2D and FIG. 3A, the gate electrode 103, the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 111, and the pair of electrodes 113 a and 113 b are formed over the substrate 101.

Next, the oxide semiconductor film 115 b is formed over the gate insulating film 105, the oxide semiconductor film 111, and the pair of electrodes 113 a and 113 b, and the gate insulating film 117 b is formed over the oxide semiconductor film 115 b. Next, the gate electrode 119 is formed over the gate insulating film 117 b.

The later steps are the same as those for the transistor 100 of Embodiment 1. Through the later steps, the transistor 100 b can be manufactured.

The manufacturing method of the transistor 100 c will be described. Through the steps of FIGS. 2A to 2D and FIG. 3A, the gate electrode 103, the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 111, and the pair of electrodes 113 a and 113 b are formed over the substrate 101.

Next, an oxide semiconductor film to be the oxide semiconductor film 115 c is formed over the gate insulating film 105, the oxide semiconductor film 111, and the pair of electrodes 113 a and 113 b, and then a mask is formed over the oxide semiconductor film by a lithography process. The oxide semiconductor film is etched using the mask to form the oxide semiconductor film 115 c. Then, the mask is removed.

Next, the gate insulating film 117 b is formed over the oxide semiconductor film 115 c. Then, the gate electrode 119 is formed over the gate insulating film 117 b.

The later steps are the same as those for the transistor 100 of Embodiment 1. Through the later steps, the transistor 100 c can be manufactured.

<Variation 2>

A transistor having different shapes of the pair of electrodes 113 a and 113 b from those of the transistor 100 illustrated in FIGS. 1A to 1C will be described with reference to FIGS. 6A to 6D.

FIGS. 6A to 6D are a top view and cross-sectional views of a transistor 100 d of a semiconductor device. FIG. 6A is a top view of the transistor 100 d, FIG. 6B is a cross-sectional view taken along dashed-dotted line A-B in FIG. 6A, FIG. 6C is a cross-sectional view taken along dashed-dotted line C-D in FIG. 6A, and FIG. 6D is a cross-sectional view taken along dashed-dotted line E-F in FIG. 6A.

FIG. 6B is a cross-sectional view in the channel length direction of the transistor 100 d, FIG. 6C is a cross-sectional view in the channel width direction of the transistor 100 d, and FIG. 6D is a cross-sectional view in the channel width direction of the transistor 100 d showing the region where the pair of electrodes and the oxide semiconductor films are stacked.

Note that in FIG. 6A, the substrate 101, the gate insulating film 105, the oxide semiconductor film 107, the gate insulating film 117, the insulating film 121, the insulating film 123, and the like are not illustrated for simplicity.

The transistor 100 d illustrated in FIGS. 6A to 6D includes a pair of electrodes 113 c and 113 d that is not in contact with the side surfaces of the oxide semiconductor film 107 and the oxide semiconductor film 111 and are in contact with the top surface of the oxide semiconductor film 111. Furthermore, the transistor 100 d includes plugs 127 a and 127 b that are in contact with the pair of electrodes 113 c and 113 d at openings 125 a and 125 b provided in the insulating film 121 and the insulating film 123.

As illustrated in FIG. 6D, since the side surfaces of the oxide semiconductor films 107 and 111 are not in contact with the pair of electrodes 113 c and 113 d in the channel width direction, electric field of the gate electrode 119 is not blocked by the pair of electrodes 113 c and 113 d. As a result, the effect of the electric field of the gate electrode 119 on the side surfaces of the oxide semiconductor films 107 and 111 can be increased, and this transistor can therefore have an excellent subthreshold swing (hereinafter referred to as S value) and a high field-effect mobility. Note that the S value is the value of a gate voltage necessary to change the on-state current by one digit; a smaller S value means better transistor characteristics.

Next, a manufacturing method of the transistor 100 d will be described with reference to FIGS. 2A to 2D and FIGS. 7A to 7C. Here, the manufacturing method of the transistor 100 d will be described with reference to cross-sectional views taken along dashed-dotted line A-B and C-D in FIG. 6A.

Through the steps of FIGS. 2A to 2C, the gate electrode 103, the insulating film 104, the oxide semiconductor film 106 b, and the oxide semiconductor film 109 a are formed over the substrate 101. Next, a conductive film 112 is formed over the oxide semiconductor film 109 a (see FIG. 7A).

The conductive film 112 can be formed by the formation method of the pair of electrodes 113 a and 113 b in Embodiment 1 as appropriate.

Next, a mask is formed over the conductive film 112 by a lithography process, and then the oxide semiconductor film 106 b, the oxide semiconductor film 109 a, and the conductive film 112 are etched using the mask to form the oxide semiconductor film 107, the oxide semiconductor film 110, and a conductive film 113. In this step, part of the insulating film 104 is also etched, so that the gate insulating film 105 is formed (see FIG. 7B).

In the etching step, the shape of the resist mask is changed, so that if etching is performed using only the resist mask without providing a hard mask, the shapes of the formed oxide semiconductor film 107 and the formed oxide semiconductor film 110 might be different from predetermined shapes. This problem arises outstandingly in micropatterning such as electron beam exposure, liquid immersion exposure, or EUV exposure. However, since the conductive film 112 provided over the oxide semiconductor film 109 a functions as a hard mask here, the oxide semiconductor film 107 and the oxide semiconductor film 110 with predetermined shapes can be obtained.

Then, a mask is formed over the conductive film 113 by a lithography process, and the conductive film 113 is etched using the mask to form the pair of electrodes 113 c and 113 d. In the case of using a positive-type photoresist as the mask, the exposing time can be shortened. In the etching step, part of the oxide semiconductor film 110 may be etched to form a depression. Here, the oxide semiconductor film having a depression is referred to as the oxide semiconductor film 111 (see FIG. 7C).

Then, by the steps similar to those of FIG. 3B, the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119 are formed. In this way, the transistor 100 d illustrated in FIGS. 6A to 6D can be manufactured.

Note that as illustrated in FIG. 28, a pair of electrodes 113 g and 113 h that is provided over the pair of electrodes 113 c and 113 d and is in contact with the side surfaces of the oxide semiconductor film 107 and the oxide semiconductor film 111 in the channel length direction of the transistor may be included. In FIG. 28, the electrode 113 g is in contact with the electrode 113 c, and the electrode 113 h is in contact with the electrode 113 d.

<Variation 3>

A transistor including an oxide semiconductor film 111 a whose shape is different from that of the oxide semiconductor film 111 included in the transistor 100 illustrated in FIGS. 1A to 1C will be described with reference to FIGS. 8A to 8C.

FIGS. 8A to 8C are a top view and cross-sectional views of a transistor 100 e of a semiconductor device. FIG. 8A is a top view of the transistor 100 e, FIG. 8B is a cross-sectional view taken along dashed-dotted line A-B in FIG. 8A, and FIG. 8C is a cross-sectional view taken along dashed-dotted line C-D in FIG. 8A.

FIG. 8B is a cross-sectional view in the channel length direction of the transistor 100 e and FIG. 8C is a cross-sectional view in the channel width direction of the transistor 100 e.

Note that in FIG. 8A, the substrate 101, the gate insulating film 105, the oxide semiconductor film 107, the gate insulating film 117, the insulating film 121, the insulating film 123, and the like are not illustrated for simplicity.

As illustrated in FIG. 8C, the transistor 100 e includes an oxide semiconductor film 111 a whose cross section in the channel width direction is substantially triangular or substantially trapezoidal. Here, the substantial triangle and the substantial trapezoid refer to the shapes in which the angle between the bottom surface in contact with the oxide semiconductor film 107 and the side surface in contact with the oxide semiconductor film 115 in the oxide semiconductor film 111 a is greater than 0° and less than or equal to 85° or greater than or equal to 30° and less than or equal to 80°. In addition, the surface on the opposite side to the bottom surface may have a sharp corner or a rounded corner. The shape may have a vertex on the opposite side to the bottom surface.

As compared with an upper region in an oxide semiconductor film whose cross section in the channel width direction is substantially rectangular, an upper region in the oxide semiconductor film 111 a whose cross section is substantially triangular or trapezoidal has a small cross-sectional area. This decreases a region having high current density on the gate insulating film 117 side. As a result, excellent S value and increased on-state current can be achieved.

A method for manufacturing the oxide semiconductor film 111 with the substantially triangular or trapezoidal cross section will be described. A mask is formed over the oxide semiconductor film 109 a illustrated in FIG. 2C by a lithography process, and then, the oxide semiconductor film 109 a is etched while the mask is made to recede. Thus, the oxide semiconductor film whose cross section in the channel width direction is substantially triangular or substantially trapezoidal as illustrated in FIG. 8C can be formed.

<Variation 4>

A transistor having a different shape of the gate electrode from that of the transistor 100 illustrated in FIGS. 1A to 1C will be described with reference to FIGS. 9A to 9C.

FIGS. 9A to 9C are a top view and cross-sectional views of a transistor 100 j of a semiconductor device. FIG. 9A is a top view of the transistor 100 j, FIG. 9B is a cross-sectional view taken along dashed-dotted line A-B in FIG. 9A, and FIG. 9C is a cross-sectional view taken along dashed-dotted line C-D in FIG. 9A.

FIG. 9B is a cross-sectional view in the channel length direction of the transistor 100 j and FIG. 9C is a cross-sectional view in the channel width direction of the transistor 100 j.

Note that in FIG. 9A, the substrate 101, the gate insulating film 105, the oxide semiconductor film 107, the gate insulating film 117, the insulating film 121, the insulating film 123, and the like are not illustrated for simplicity.

As illustrated in FIGS. 9A and 9B, the transistor 100 j is characterized in that the pair of electrodes 113 a and 113 b does not overlap with a gate electrode 119 a in the channel length direction. As a result, parasitic capacitance between the pair of electrodes 113 a and 113 b and the gate electrode 119 a can be reduced, so that the on-state current of the transistor can be increased.

After the gate electrode 119 a is formed, it is preferable to form impurity regions 111 e and 111 f by adding impurities to the oxide semiconductor film 111 using the gate electrode 119 a and the pair of electrodes 113 a and 113 b as masks. As a result, the on-state current of the transistor can be increased. Note that as the impurities added to the oxide semiconductor film 111, hydrogen, helium, neon, argon, krypton, xenon, boron, nitrogen, phosphorus, or arsenic can be used.

As illustrated in FIG. 32A, a gate electrode 119 b with a tapered shape may be included. In this case, depending on the manufacturing conditions, the impurity regions 111 e and 111 f might be formed to have tapered shapes owing to the tapered shape of the gate electrode 119 b. Note that in FIG. 32A, part of end portions of the impurity regions 111 e and 111 f is located at the interface between the oxide semiconductor film 107 and the oxide semiconductor film 111. Furthermore, depending on the manufacturing conditions, as illustrated in FIG. 32B, the end portions of the impurity regions 111 e and 111 f may be located not at the interface between the oxide semiconductor film 107 and the oxide semiconductor film 111 but inside the oxide semiconductor film 111.

The structures, methods, and the like described in this embodiment can be used as appropriate in combination with any of the structures, methods, and the like described in the other embodiments and examples.

Embodiment 2

In this embodiment, a method for reducing oxygen vacancies in an oxide semiconductor film, which is different from the method in Embodiment 1, will be described. This embodiment is different from Embodiment 1 in adding oxygen to an oxide semiconductor film positioned over the pair of electrodes 113 a and 113 b.

As illustrated in FIG. 10A, the gate electrode 103 is formed over the substrate 101, and the insulating film 104 is formed over the gate electrode 103. Then, the oxide semiconductor film 106 is formed over the insulating film 104, and the oxide semiconductor film 109 is formed over the oxide semiconductor film 106.

Next, a mask is formed over the oxide semiconductor film 109 by a lithography process, and part of the insulating film 104, part of the oxide semiconductor film 106, and part of the oxide semiconductor film 109 are etched using the mask; thus, the gate insulating film 105, the oxide semiconductor film 107, and an oxide semiconductor film 110 a are formed as illustrated in FIG. 10B.

Next, heat treatment may be performed to release water, hydrogen, and the like contained in the oxide semiconductor film 109. This heat treatment may be skipped and water, hydrogen, and the like contained in the oxide semiconductor film 109 may be released by heat treatment performed in a later step.

Next, the pair of electrodes 113 a and 113 b is formed over the oxide semiconductor film 110 a. After the pair of electrodes 113 a and 113 b is formed, cleaning treatment is preferably performed to remove an etching residue. A short circuit of the pair of electrodes 113 a and 113 b can be suppressed by this cleaning treatment. By the cleaning treatment, an oxide semiconductor film 111 b part of which is etched is formed (see FIG. 10C).

Next, as illustrated in FIG. 10D, an oxide semiconductor film 114 is formed over the gate insulating film 105, the oxide semiconductor film 111 b, and the pair of electrodes 113 a and 113 b. Next, oxygen 108 is added to the oxide semiconductor film 114.

As the oxygen 108 added to the oxide semiconductor film 114, at least one kind selected from oxygen radicals, oxygen atoms, oxygen atomic ions, oxygen molecular ions, and the like is used. As a method for adding the oxygen 108 to the oxide semiconductor film 114, an ion doping method, an ion implantation method, or the like can be used.

In the case of adding oxygen to the oxide semiconductor film 114, it is preferable that oxygen be added to the oxide semiconductor film 114 so that a peak of the concentration profile of oxygen atomic ions is positioned in the oxide semiconductor film 114. In the case where the oxide semiconductor film 114 is thin, oxygen might enter the oxide semiconductor film 111 b; however, by using such conditions as to make a peak of the concentration profile of oxygen atomic ions be positioned in the oxide semiconductor film 114, damage to the oxide semiconductor film 111 b can be reduced. In other words, defects in the oxide semiconductor film 111 b can be reduced, so that variations in electrical characteristics of the transistor can be reduced. Furthermore, in the case where oxygen is added to the oxide semiconductor film 114 so that the amount of added oxygen atoms at the interface between the insulating film 104 and the oxide semiconductor film 111 b is less than 1×10²¹ atoms/cm³, less than 1×10²⁰ atoms/cm³, or less than 1×10¹⁹ atoms/cm³, damage to the oxide semiconductor film 111 b can be reduced by later heat treatment, whereby variations in electrical characteristics of the transistor can be reduced.

In the case of using an ion implantation method as the method for adding the oxygen 108, damage to the oxide semiconductor film 114 can be reduced by using oxygen molecular ions as the oxygen 108 added to the oxide semiconductor film 114.

Oxygen may be added to the oxide semiconductor film 114 by plasma treatment in which the oxide semiconductor film 114 is exposed to plasma generated in an atmosphere containing oxygen.

Through the above-described steps, an oxide semiconductor film 114 a to which oxygen is added, which is illustrated in FIG. 11A, can be formed.

Next, heat treatment is performed so that part of oxygen contained in the oxide semiconductor film 114 a to which oxygen is added can be transferred to the oxide semiconductor film 111 b; consequently, oxygen vacancies in the oxide semiconductor film 111 b can be reduced. This oxide semiconductor film with reduced oxygen vacancies is represented as the oxide semiconductor film 111 c in FIG. 11B. Oxygen vacancies in the oxide semiconductor film 114 a to which oxygen is added can be reduced. This oxide semiconductor film is represented as the oxide semiconductor film 114 b in FIG. 11B.

Through the above-described steps, oxygen vacancies in the oxide semiconductor films can be reduced. The oxide semiconductor films can have low density of localized states.

Then, part of the oxide semiconductor film 114 b is etched in a manner similar to that of Embodiment 1, so that an oxide semiconductor film 115 d can be formed. Furthermore, the gate insulating film 117 and the gate electrode 119 can be formed (see FIG. 11C). Moreover, the insulating film 121 and the insulating film 123 can be formed.

Through the above-described steps, the density of localized states of the oxide semiconductor films is lowered, and thus a transistor with excellent electrical characteristics can be manufactured. In addition, a highly reliable transistor with few variations with time in electrical characteristics or few variations in electrical characteristics due to a stress test can be manufactured.

<Variation 1>

A method for adding oxygen to the oxide semiconductor film 114, which is different from the above-described method in Embodiment 2, will be described with reference to FIGS. 12A to 12C.

In a manner similar to that of the above-described method in Embodiment 2, the gate electrode 103, the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 111 b, the pair of electrodes 113 a and 113 b, and the oxide semiconductor film 114 are formed over the substrate 101. Next, the insulating film 116 is formed over the oxide semiconductor film 114. Then, the oxygen 108 is added to the oxide semiconductor film 114 through the insulating film 116 (see FIG. 12A).

Oxygen may be added to the oxide semiconductor film 114 through the insulating film 116 by plasma treatment in which the insulating film 116 is exposed to plasma generated in an atmosphere containing oxygen.

Through the above-described steps, the oxide semiconductor film 114 a to which oxygen is added and an insulating film 116 a to which oxygen is added, which are illustrated in FIG. 12B, can be formed.

Next, heat treatment is performed so that part of oxygen contained in the oxide semiconductor film 114 a to which oxygen is added and the insulating film 116 a to which oxygen is added can be transferred to the oxide semiconductor film 111 b; consequently, oxygen vacancies in the oxide semiconductor film 111 b can be reduced. This oxide semiconductor film with reduced oxygen vacancies is represented as the oxide semiconductor film 111 c in FIG. 12C. Oxygen vacancies in the oxide semiconductor film 114 a to which oxygen is added can be reduced. This oxide semiconductor film is represented as the oxide semiconductor film 114 b in FIG. 12C. Defects in the insulating film 116 a to which oxygen is added can be reduced. This insulating film is represented as the oxide semiconductor film 116 b in FIG. 12C.

Through the above-described steps, oxygen vacancies in the oxide semiconductor films can be reduced. The oxide semiconductors film can have low density of localized states.

Then, part of the oxide semiconductor film 114 b is etched in a manner similar to that of Embodiment 1, so that the oxide semiconductor film 115 a can be formed. In addition, part of the insulating film 116 b is etched, so that the gate insulating film 117 can be formed. Furthermore, the gate electrode 119 can be formed. Moreover, the insulating film 121 and the insulating film 123 can be formed.

Through the above-described steps, the density of localized states of the oxide semiconductor films is lowered, and thus a transistor with excellent electrical characteristics can be manufactured. In addition, a highly reliable transistor with few variations with time in electrical characteristics or few variations in electrical characteristics due to a stress test can be manufactured.

The structures, methods, and the like described in this embodiment can be used as appropriate in combination with any of the structures, methods, and the like described in the other embodiments and examples.

Embodiment 3

Transistors each having a stacked structure of oxide semiconductor films different from that of the transistor 100 illustrated in FIGS. 1A to 1C will be described with reference to FIGS. 13A to 13C.

A transistor 100 f illustrated in FIG. 13A is different from the transistor 100 illustrated in FIG. 1B in not including the oxide semiconductor film 115. In other words, the transistor 100 f is characterized by including the gate insulating film 117 that is in contact with the oxide semiconductor film 111, the pair of electrodes 113 a and 113 b, and the gate electrode 119.

Note that in a method for manufacturing the transistor 100 f illustrated in FIG. 13A, the method for forming the oxide semiconductor film 111 described in Embodiment 1 can be used as appropriate.

A transistor 100 g illustrated in FIG. 13B is different from the transistor 100 illustrated in FIG. 1B in not including the oxide semiconductor film 107. In other words, the transistor 100 g is characterized by including the gate insulating film 105 that is in contact with the gate electrode 103 and the oxide semiconductor film 111.

Note that in a method for manufacturing the transistor 100 g illustrated in FIG. 13B, the method for forming the oxide semiconductor film 111 c described in Embodiment 2 can be used as appropriate.

A transistor 100 h illustrated in FIG. 13C is different from the transistor 100 illustrated in FIG. 1B in including an oxide semiconductor film 115 e between the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b. In other words, the transistor 100 h is characterized by including the oxide semiconductor film 115 e that is in contact with the oxide semiconductor film 111, the pair of electrodes 113 a and 113 b, and the gate insulating film 117. The oxide semiconductor film 115 e is provided between the oxide semiconductor film 111 and the pair of electrodes 113 a and 113 b.

Note that in a method for manufacturing the transistor 100 h illustrated in FIG. 13C, the method for forming the oxide semiconductor film 111 described in Embodiment 1 and/or Embodiment 2 can be used as appropriate.

The transistor of one embodiment of the present invention can have various cross-sectional structures.

For example, as illustrated in FIG. 33A, the transistor 100 f may include the gate electrode 119 a that does not overlap with the pair of electrodes 113 a and 113 b in the channel length direction. In this case, the oxide semiconductor film 107 and the oxide semiconductor film 111 may each include the impurity regions 111 e and 111 f.

As illustrated in FIG. 33B, the transistor 100 f may include the gate electrode 119 b having a tapered shape. In this case, the impurity regions 111 e and 111 f that partly overlap with the gate electrode 119 b may be included. The end portions of the impurity regions 111 e and 111 f may be located at the interface between the oxide semiconductor film 107 and the oxide semiconductor film 111 or inside the oxide semiconductor film 111.

For example, as illustrated in FIG. 33C, the transistor 100 g may include the gate electrode 119 a that does not overlap with the pair of electrodes 113 a and 113 b in the channel length direction. In this case, the oxide semiconductor film 111 and the oxide semiconductor film 115 a may each include the impurity regions 111 e and 111 f.

As illustrated in FIG. 33D, the transistor 100 g may include the gate electrode 119 b having a tapered shape. In this case, the impurity regions 111 e and 111 f that partly overlap with the gate electrode 119 b may be included. The end portions of the impurity regions 111 e and 111 f may be located at the interface between the oxide semiconductor film 107 and the oxide semiconductor film 111 or inside the oxide semiconductor film 111.

As illustrated in FIG. 34A, the transistor 100 h may have a structure in which the end portions of the pair of electrodes 113 a and 113 b are each substantially aligned with an end portion of a gate electrode 119 c. In this case, it is not necessary to provide the impurity regions 111 e and 111 f.

As illustrated in FIG. 34B, the transistor 100 h may include the gate electrode 119 c that does not overlap with the pair of electrodes 113 a and 113 b in the channel length direction. In this case, the oxide semiconductor film 107, the oxide semiconductor film 111, and the oxide semiconductor film 115 b may each include the impurity regions 111 e and 111 f.

As illustrated in FIG. 34C, the transistor 100 h may include the gate electrode 119 b having a tapered shape. In this case, the impurity regions 111 e and 111 f that partly overlap with the gate electrode 119 b may be included.

As illustrated in FIG. 34D, the end portions of the impurity regions 111 e and 111 f may be located inside the oxide semiconductor film 111.

As described above, the transistor of one embodiment of the present invention can have various structures depending on whether the oxide semiconductor films such as the oxide semiconductor films 107, 111, and 115 are provided, the place to provide the oxide semiconductor films, the shape of the gate electrode, whether the impurity regions are provided, the shape of the impurity regions, and the like. Accordingly, the structures illustrated in FIGS. 32A and 32B, FIGS. 33A to 33D, and FIGS. 34A to 34D can be applied as appropriate to the other drawings described in this specification.

The structures, methods, and the like described in this embodiment can be used as appropriate in combination with any of the structures, methods, and the like described in the other embodiments and examples.

Embodiment 4

In this embodiment, a structure and a manufacturing method of a transistor with is different from the transistors described in Embodiments 1 to 3 in the positional relation between the gate electrode and the pair of electrodes and in the shape of the gate electrode will be described with reference to FIGS. 14A to 14C, FIGS. 15A to 15C, and FIGS. 16A to 16C.

FIGS. 14A to 14C are a top view and cross-sectional views of a transistor 100 i of a semiconductor device. FIG. 14A is a top view of the transistor 100 i, FIG. 14B is a cross-sectional view of the transistor 100 i taken along dashed-dotted line A-B in FIG. 14A, and FIG. 14C is a cross-sectional view of the transistor 100 i taken along dashed-dotted line C-D in FIG. 14A. Note that in FIG. 14A, the substrate 101, an insulating film 102, a gate insulating film 105 b, the oxide semiconductor film 107, the oxide semiconductor film 115, the gate insulating film 117, the insulating film 121, the insulating film 123, and the like are not illustrated for simplicity.

In the transistor 100 i illustrated in FIGS. 14A to 14C, a gate electrode 103 a is formed over the insulating film 102. The gate insulating film 105 b that is isolated is formed over the insulating film 102 and the gate electrode 103 a. As illustrated in FIG. 14B, a pair of electrodes 113 e and 113 f covers part of the top surface of the oxide semiconductor film 111 and side surfaces of the gate insulating film 105 b, the oxide semiconductor film 107, and the oxide semiconductor film 111 in the channel length direction. As illustrated in FIG. 14C, the oxide semiconductor film 115 covers part of a top surface and part of the side surface of the gate insulating film 105 b, the side surface of the oxide semiconductor film 107, and the top and side surfaces of the oxide semiconductor film 111 in the channel width direction.

In other words, the transistor illustrated in FIG. 14B is characterized in that the pair of electrodes 113 e and 113 f surrounds side surfaces of the gate electrode 103 a as well as the gate insulating film 105 b, the oxide semiconductor film 107, and the oxide semiconductor film 111 in the channel length direction.

In the transistor 100 i, because the gate electrode 103 a is isolated and the gate electrode 103 a is covered with the gate insulating film 105 b, it is preferable that a wiring 129 and the gate electrode 103 a that are formed over the substrate 101 be connected to each other through an opening 131 provided in the insulating film 102 (see FIG. 14C).

The wiring 129 can be formed using any of the materials that can be used as the material of the gate electrode 103 or the pair of electrodes 113 a and 113 b described in Embodiment 1.

When the insulating film 102 is formed using a material that has a different etching rate from the insulating film 104, typically a material having a lower etching rate than the insulating film 104, the insulating film 102 functions as an etching stop film. As a result, the isolated gate insulating film 105 b can be formed.

Next, a manufacturing method of the transistor 100 i will be described with reference to FIGS. 2A to 2D, FIGS. 15A to 15C, and FIGS. 16A to 16C. Here, the manufacturing method of the transistor 100 i will be described with reference to cross-sectional views taken along A-B and C-D in FIG. 15A.

As illustrated in FIG. 15A, the wiring 129 is formed over the substrate 101.

The wiring 129 can be formed using any of the methods for forming the pair of electrodes 113 a and 113 b described in Embodiment 1 as appropriate.

Next, the insulating film 102 is formed over the substrate 101 and the wiring 129.

The insulating film 102 can be formed using any of the methods for forming the insulating film 104 described in Embodiment 1 as appropriate.

Next, an opening is formed in the insulating film 102, and then the gate electrode 103 a, the insulating film 104, the oxide semiconductor film 106 b, and the oxide semiconductor film 109 a are formed over the insulating film 102 through the steps illustrated in FIGS. 2A to 2C.

Next, a mask is formed over the oxide semiconductor film 109 a by a lithography process. Then, the insulating film 104, the oxide semiconductor film 106 b, and the oxide semiconductor film 109 a are each etched using the mask, so that an insulating film 105 c, an oxide semiconductor film 107 a, and the oxide semiconductor film 110 a are formed (see FIG. 15B).

When the insulating film 102 is formed using a material that has a different etching rate from the insulating film 104, typically a material having a lower etching rate than the insulating film 104, the insulating film 102 functions as an etching stop film. As a result, etching of the insulating film 102 can be prevented in the step of etching the insulating film 104. When the insulating film 102 is formed using a material having substantially the same etching rate as that of the insulating film 104, not only the insulating film 104 but also the insulating film 102 is etched, so that the insulating film 105 c and an insulating film having a projection in a region covered with the insulating film 105 c are formed.

Next, a mask is formed over the oxide semiconductor film 110 a by a lithography process. Then, part of the oxide semiconductor film 107 a, part of the oxide semiconductor film 110 a, and part of the insulating film 105 c are etched using the mask; thus, the gate insulating film 105 b, an oxide semiconductor film 107 b, and an oxide semiconductor film 110 b are formed (see FIG. 15C). Here, at least the oxide semiconductor film 107 a, the oxide semiconductor film 110 a, and the gate insulating film 105 c in the channel width direction are etched. As a result, a transistor with the s-channel structure can be formed. Since the gate electrode 103 a is covered with the gate insulating film 105 b, a short circuit between the pair of electrodes 113 e and 113 f, which are to be formed later, and the gate electrode 103 a can be prevented.

Next, the pair of electrodes 113 e and 113 f is formed over the oxide semiconductor film 110 b. After the pair of electrodes 113 e and 113 f is formed, cleaning treatment is preferably performed to remove an etching residue. A short circuit of the pair of electrodes 113 e and 113 f can be suppressed by this cleaning treatment. By the cleaning treatment, an oxide semiconductor film 111 d part of which is etched is formed (see FIG. 16A).

Next, as illustrated in FIG. 16B, the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119 can be formed over the insulating film 102, the gate insulating film 105 b, the oxide semiconductor film 111 b, and the pair of electrodes 113 e and 113 f.

Then, as illustrated in FIG. 16C, the insulating film 121 and the insulating film 123 can be formed.

Through the above-described steps, the density of localized states of the oxide semiconductor films is lowered, and thus a transistor with excellent electrical characteristics can be manufactured. In addition, a highly reliable transistor with few variations with time in electrical characteristics or few variations in electrical characteristics due to a stress test can be manufactured.

The structures, methods, and the like described in this embodiment can be used as appropriate in combination with any of the structures, methods, and the like described in the other embodiments and examples.

Embodiment 5

In this embodiment, the oxide semiconductor film is described.

<Structure of Oxide Semiconductor>

A structure of an oxide semiconductor is described below.

An oxide semiconductor is classified into a single crystal oxide semiconductor and a non-single-crystal oxide semiconductor. Examples of a non-single-crystal oxide semiconductor include a c-axis aligned crystalline oxide semiconductor (CAAC-OS), a polycrystalline oxide semiconductor, a microcrystalline oxide semiconductor, and an amorphous oxide semiconductor.

From another perspective, an oxide semiconductor is classified into an amorphous oxide semiconductor and a crystalline oxide semiconductor. Examples of a crystalline oxide semiconductor include a single crystal oxide semiconductor, a CAAC-OS, a polycrystalline oxide semiconductor, and a microcrystalline oxide semiconductor.

<CAAC-OS>

First, a CAAC-OS is described. Note that a CAAC-OS can be referred to as an oxide semiconductor including c-axis aligned nanocrystals (CANC).

A CAAC-OS is one of oxide semiconductors having a plurality of c-axis aligned crystal parts (also referred to as pellets).

In a combined analysis image (also referred to as a high-resolution TEM image) of a bright-field image and a diffraction pattern of a CAAC-OS, which is obtained using a transmission electron microscope (TEM), a plurality of pellets can be observed. However, in the high-resolution TEM image, a boundary between pellets, that is, a grain boundary is not clearly observed. Thus, in the CAAC-OS, a reduction in electron mobility due to the grain boundary is less likely to occur.

A CAAC-OS observed with TEM is described below. FIG. 17A shows a high-resolution TEM image of a cross section of the CAAC-OS which is observed from a direction substantially parallel to the sample surface. The high-resolution TEM image is obtained with a spherical aberration corrector function. The high-resolution TEM image obtained with a spherical aberration corrector function is particularly referred to as a Cs-corrected high-resolution TEM image. The Cs-corrected high-resolution TEM image can be obtained with, for example, an atomic resolution analytical electron microscope JEM-ARM200F manufactured by JEOL Ltd.

FIG. 17B is an enlarged Cs-corrected high-resolution TEM image of a region (1) in FIG. 17A. FIG. 17B shows that metal atoms are arranged in a layered manner in a pellet. Each metal atom layer has a configuration reflecting unevenness of a surface over which the CAAC-OS is formed (hereinafter, the surface is referred to as a formation surface) or a top surface of the CAAC-OS, and is arranged parallel to the formation surface or the top surface of the CAAC-OS.

As shown in FIG. 17B, the CAAC-OS has a characteristic atomic arrangement. The characteristic atomic arrangement is denoted by an auxiliary line in FIG. 17C. FIGS. 17B and 17C prove that the size of a pellet is approximately 1 nm to 3 nm, and the size of a space caused by tilt of the pellets is approximately 0.8 nm. Therefore, the pellet can also be referred to as a nanocrystal (nc).

Here, according to the Cs-corrected high-resolution TEM images, the schematic arrangement of pellets 5100 of a CAAC-OS over a substrate 5120 is illustrated by such a structure in which bricks or blocks are stacked (see FIG. 17D). The part in which the pellets are tilted as observed in FIG. 17C corresponds to a region 5161 shown in FIG. 17D.

FIG. 18A shows a Cs-corrected high-resolution TEM image of a plane of the CAAC-OS observed from a direction substantially perpendicular to the sample surface. FIGS. 18B, 18C, and 18D are enlarged Cs-corrected high-resolution TEM images of regions (1), (2), and (3) in FIG. 18A, respectively. FIGS. 18B, 18C, and 18D indicate that metal atoms are arranged in a triangular, quadrangular, or hexagonal configuration in a pellet. However, there is no regularity of arrangement of metal atoms between different pellets.

Next, a CAAC-OS analyzed by X-ray diffraction (XRD) is described. For example, when the structure of a CAAC-OS including an InGaZnO₄ crystal is analyzed by an out-of-plane method, a peak appears at a diffraction angle (2θ) of around 31° as shown in FIG. 19A. This peak is derived from the (009) plane of the InGaZnO₄ crystal, which indicates that crystals in the CAAC-OS have c-axis alignment, and that the c-axes are aligned in a direction substantially perpendicular to the formation surface or the top surface of the CAAC-OS.

Note that in structural analysis of the CAAC-OS by an out-of-plane method, another peak may appear when 2θ is around 36°, in addition to the peak at 2θ of around 31°. The peak at 2θ of around 36° indicates that a crystal having no c-axis alignment is included in part of the CAAC-OS. It is preferable that in the CAAC-OS analyzed by an out-of-plane method, a peak appear when 2θ is around 31° and that a peak not appear when 2θ is around 36°.

On the other hand, in structural analysis of the CAAC-OS by an in-plane method in which an X-ray is incident on a sample in a direction substantially perpendicular to the c-axis, a peak appears when 2θ is around 56°. This peak is attributed to the (110) plane of the InGaZnO₄ crystal. In the case of the CAAC-OS, when analysis (φ scan) is performed with 2θ fixed at around 56° and with the sample rotated using a normal vector of the sample surface as an axis (φ axis), as shown in FIG. 19B, a peak is not clearly observed. In contrast, in the case of a single crystal oxide semiconductor of InGaZnO₄, when φ scan is performed with 2θ fixed at around 56°, as shown in FIG. 19C, six peaks which are derived from crystal planes equivalent to the (110) plane are observed. Accordingly, the structural analysis using XRD shows that the directions of a-axes and b-axes are different in the CAAC-OS.

Next, a CAAC-OS analyzed by electron diffraction is described. For example, when an electron beam with a probe diameter of 300 nm is incident on a CAAC-OS including an InGaZnO₄ crystal in a direction parallel to the sample surface, a diffraction pattern (also referred to as a selected-area transmission electron diffraction pattern) shown in FIG. 35A might be obtained. In this diffraction pattern, spots derived from the (009) plane of an InGaZnO₄ crystal are included. Thus, the electron diffraction also indicates that pellets included in the CAAC-OS have c-axis alignment and that the c-axes are aligned in a direction substantially perpendicular to the formation surface or the top surface of the CAAC-OS. Meanwhile, FIG. 35B shows a diffraction pattern obtained in such a manner that an electron beam with a probe diameter of 300 nm is incident on the same sample in a direction perpendicular to the sample surface. As shown in FIG. 35B, a ring-like diffraction pattern is observed. Thus, the electron diffraction also indicates that the a-axes and b-axes of the pellets included in the CAAC-OS do not have regular alignment. The first ring in FIG. 35B is considered to be derived from the (010) plane, the (100) plane, and the like of the InGaZnO₄ crystal. The second ring in FIG. 35B is considered to be derived from the (110) plane and the like.

Moreover, the CAAC-OS is an oxide semiconductor having a low density of defect states. Defects in the oxide semiconductor are, for example, a defect due to impurity and oxygen vacancies. Therefore, the CAAC-OS can be regarded as an oxide semiconductor with a low impurity concentration, or an oxide semiconductor having a small number of oxygen vacancies.

The impurity contained in the oxide semiconductor might serve as a carrier trap or serve as a carrier generation source. Furthermore, oxygen vacancies in the oxide semiconductor serve as carrier traps or serve as carrier generation sources when hydrogen is captured therein.

Note that the impurity means an element other than the main components of the oxide semiconductor, such as hydrogen, carbon, silicon, or a transition metal element. For example, an element (specifically, silicon or the like) having higher strength of bonding to oxygen than a metal element included in an oxide semiconductor extracts oxygen from the oxide semiconductor, which results in disorder of the atomic arrangement and reduced crystallinity of the oxide semiconductor. A heavy metal such as iron or nickel, argon, carbon dioxide, or the like has a large atomic radius (or molecular radius), and thus disturbs the atomic arrangement of the oxide semiconductor and decreases crystallinity.

An oxide semiconductor having a low density of defect states (a small number of oxygen vacancies) can have a low carrier density. Such an oxide semiconductor is referred to as a highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor. A CAAC-OS has a low impurity concentration and a low density of defect states. That is, a CAAC-OS is likely to be highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor. Thus, a transistor including a CAAC-OS rarely has negative threshold voltage (is rarely normally on). The highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor has few carrier traps. An electric charge trapped by the carrier traps in the oxide semiconductor takes a long time to be released. The trapped electric charge may behave like a fixed electric charge. Thus, the transistor which includes the oxide semiconductor having a high impurity concentration and a high density of defect states might have unstable electrical characteristics. However, a transistor including a CAAC-OS has small variation in electrical characteristics and high reliability.

Since the CAAC-OS has a low density of defect states, carriers generated by light irradiation or the like are less likely to be trapped in defect states. Therefore, in a transistor using the CAAC-OS, change in electrical characteristics due to irradiation with visible light or ultraviolet light is small.

<Microcrystalline Oxide Semiconductor>

Next, a microcrystalline oxide semiconductor is described.

A microcrystalline oxide semiconductor has a region in which a crystal part is observed and a region in which a crystal part is not clearly observed in a high-resolution TEM image. In most cases, the size of a crystal part included in the microcrystalline oxide semiconductor is greater than or equal to 1 nm and less than or equal to 100 nm, or greater than or equal to 1 nm and less than or equal to 10 nm. An oxide semiconductor including a nanocrystal (nc) that is a microcrystal with a size greater than or equal to 1 nm and less than or equal to 10 nm, or a size greater than or equal to 1 nm and less than or equal to 3 nm is specifically referred to as a nanocrystalline oxide semiconductor (nc-OS). In a high-resolution TEM image of the nc-OS, for example, a grain boundary is not clearly observed in some cases. Note that there is a possibility that the origin of the nanocrystal is the same as that of a pellet in a CAAC-OS. Therefore, a crystal part of the nc-OS may be referred to as a pellet in the following description.

In the nc-OS, a microscopic region (for example, a region with a size greater than or equal to 1 nm and less than or equal to 10 nm, in particular, a region with a size greater than or equal to 1 nm and less than or equal to 3 nm) has a periodic atomic arrangement. There is no regularity of crystal orientation between different pellets in the nc-OS. Thus, the orientation of the whole film is not ordered. Accordingly, the nc-OS cannot be distinguished from an amorphous oxide semiconductor, depending on an analysis method. For example, when the nc-OS is subjected to structural analysis by an out-of-plane method with an XRD apparatus using an X-ray having a diameter larger than the size of a pellet, a peak which shows a crystal plane does not appear. Furthermore, a diffraction pattern like a halo pattern is observed when the nc-OS is subjected to electron diffraction using an electron beam with a probe diameter (e.g., 50 nm or larger) that is larger than the size of a pellet (the electron diffraction is also referred to as selected-area electron diffraction). Meanwhile, spots appear in a nanobeam electron diffraction pattern of the nc-OS when an electron beam having a probe diameter close to or smaller than the size of a pellet is applied. Moreover, in a nanobeam electron diffraction pattern of the nc-OS, regions with high luminance in a circular (ring) pattern are shown in some cases. Also in a nanobeam electron diffraction pattern of the nc-OS, a plurality of spots is shown in a ring-like region in some cases.

Since there is no regularity of crystal orientation between the pellets (nanocrystals) as mentioned above, the nc-OS can also be referred to as an oxide semiconductor including random aligned nanocrystals (RANC) or an oxide semiconductor including non-aligned nanocrystals (NANC).

The nc-OS is an oxide semiconductor that has high regularity as compared with an amorphous oxide semiconductor. Therefore, the nc-OS is likely to have a lower density of defect states than an amorphous oxide semiconductor. Note that there is no regularity of crystal orientation between different pellets in the nc-OS. Therefore, the nc-OS has a higher density of defect states than the CAAC-OS.

<Amorphous Oxide Semiconductor>

Next, an amorphous oxide semiconductor is described.

The amorphous oxide semiconductor is an oxide semiconductor having disordered atomic arrangement and no crystal part and exemplified by an oxide semiconductor which exists in an amorphous state as quartz.

In a high-resolution TEM image of the amorphous oxide semiconductor, crystal parts cannot be found.

When the amorphous oxide semiconductor is subjected to structural analysis by an out-of-plane method with an XRD apparatus, a peak which shows a crystal plane does not appear. A halo pattern is observed when the amorphous oxide semiconductor is subjected to electron diffraction. Furthermore, a spot is not observed and only a halo pattern appears when the amorphous oxide semiconductor is subjected to nanobeam electron diffraction.

There are various understandings of an amorphous structure. For example, a structure whose atomic arrangement does not have ordering at all is called a completely amorphous structure. Meanwhile, a structure which has ordering until the nearest neighbor atomic distance or the second-nearest neighbor atomic distance but does not have long-range ordering is also called an amorphous structure. Therefore, the strictest definition does not permit an oxide semiconductor to be called an amorphous oxide semiconductor as long as even a negligible degree of ordering is present in an atomic arrangement. At least an oxide semiconductor having long-term ordering cannot be called an amorphous oxide semiconductor. Accordingly, because of the presence of crystal part, for example, a CAAC-OS and an nc-OS cannot be called an amorphous oxide semiconductor or a completely amorphous oxide semiconductor.

<Amorphous-Like Oxide Semiconductor>

Note that an oxide semiconductor may have a structure intermediate between the nc-OS and the amorphous oxide semiconductor. The oxide semiconductor having such a structure is specifically referred to as an amorphous-like oxide semiconductor (a-like OS).

In a high-resolution TEM image of the a-like OS, a void may be observed. Furthermore, in the high-resolution TEM image, there are a region where a crystal part is clearly observed and a region where a crystal part is not observed.

The a-like OS has an unstable structure because it includes a void. To verify that an a-like OS has an unstable structure as compared with a CAAC-OS and an nc-OS, a change in structure caused by electron irradiation is described below.

An a-like OS (referred to as Sample A), an nc-OS (referred to as Sample B), and a CAAC-OS (referred to as Sample C) are prepared as samples subjected to electron irradiation. Each of the samples is an In—Ga—Zn oxide.

First, a high-resolution cross-sectional TEM image of each sample is obtained. The high-resolution cross-sectional TEM images show that all the samples have crystal parts.

Note that which part is regarded as a crystal part is determined as follows. It is known that a unit cell of an InGaZnO₄ crystal has a structure in which nine layers including three In—O layers and six Ga—Zn—O layers are stacked in the c-axis direction. The distance between the adjacent layers is equivalent to the lattice spacing on the (009) plane (also referred to as d value). The value is calculated to be 0.29 nm from crystal structural analysis. Accordingly, a portion where the lattice spacing between lattice fringes is greater than or equal to 0.28 nm and less than or equal to 0.30 nm is regarded as a crystal part of InGaZnO₄. Each of lattice fringes corresponds to the a-b plane of the InGaZnO₄ crystal.

FIG. 36 shows change in the average size of crystal parts (at 22 points to 45 points) in each sample. Note that the crystal part size corresponds to the length of a lattice fringe. FIG. 36 indicates that the crystal part size in the a-like OS increases with an increase in the cumulative electron dose. Specifically, as shown by (1) in FIG. 36, a crystal part of approximately 1.2 nm (also referred to as an initial nucleus) at the start of TEM observation grows to a size of approximately 2.6 nm at a cumulative electron dose of 4.2×10⁸ e⁻/nm². In contrast, the crystal part size in the nc-OS and the CAAC-OS shows little change from the start of electron irradiation to a cumulative electron dose of 4.2×10⁸ e⁻/nm². Specifically, as shown by (2) and (3) in FIG. 36, the average crystal sizes in an nc-OS and a CAAC-OS are approximately 1.4 nm and approximately 2.1 nm, respectively, regardless of the cumulative electron dose.

In this manner, growth of the crystal part in the a-like OS is induced by electron irradiation. In contrast, in the nc-OS and the CAAC-OS, growth of the crystal part is hardly induced by electron irradiation. Therefore, the a-like OS has an unstable structure as compared with the nc-OS and the CAAC-OS.

The a-like OS has a lower density than the nc-OS and the CAAC-OS because it includes a void. Specifically, the density of the a-like OS is higher than or equal to 78.6% and lower than 92.3% of the density of the single crystal oxide semiconductor having the same composition. The density of each of the nc-OS and the CAAC-OS is higher than or equal to 92.3% and lower than 100% of the density of the single crystal oxide semiconductor having the same composition. Note that it is difficult to deposit an oxide semiconductor having a density of lower than 78% of the density of the single crystal oxide semiconductor.

For example, in the case of an oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of single crystal InGaZnO₄ with a rhombohedral crystal structure is 6.357 g/cm³. Accordingly, in the case of the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of the a-like OS is higher than or equal to 5.0 g/cm³ and lower than 5.9 g/cm³. For example, in the case of the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of each of the nc-OS and the CAAC-OS is higher than or equal to 5.9 g/cm³ and lower than 6.3 g/cm³.

Note that there is a possibility that an oxide semiconductor having a certain composition cannot exist in a single crystal structure. In that case, single crystal oxide semiconductors with different compositions are combined at an adequate ratio, which makes it possible to calculate density equivalent to that of a single crystal oxide semiconductor with the desired composition. The density of a single crystal oxide semiconductor having the desired composition can be calculated using a weighted average according to the combination ratio of the single crystal oxide semiconductors with different compositions. Note that it is preferable to use as few kinds of single crystal oxide semiconductors as possible to calculate the density.

As described above, oxide semiconductors have various structures and various properties. Note that an oxide semiconductor may be a stacked layer including two or more films of an amorphous oxide semiconductor, an a-like OS, a microcrystalline oxide semiconductor, and a CAAC-OS, for example.

<Deposition Model>

Examples of deposition models of a CAAC-OS and an nc-OS are described below.

FIG. 37A is a schematic view of the inside of a deposition chamber where a CAAC-OS is deposited by a sputtering method.

A target 5130 is attached to a backing plate. A plurality of magnets is provided to face the target 5130 with the backing plate positioned therebetween. The plurality of magnets generates a magnetic field. A sputtering method in which the disposition rate is increased by utilizing a magnetic field of magnets is referred to as a magnetron sputtering method.

The substrate 5120 is placed to face the target 5130, and the distance d (also referred to as a target-substrate distance (T-S distance)) is greater than or equal to 0.01 m and less than or equal to 1 m, preferably greater than or equal to 0.02 m and less than or equal to 0.5 m. The deposition chamber is mostly filled with a deposition gas (e.g., an oxygen gas, an argon gas, or a mixed gas containing oxygen at 5 vol % or higher) and the pressure in the deposition chamber is controlled to be higher than or equal to 0.01 Pa and lower than or equal to 100 Pa, preferably higher than or equal to 0.1 Pa and lower than or equal to 10 Pa. Here, discharge starts by application of a voltage at a certain value or higher to the target 5130, and plasma is observed. The magnetic field forms a high-density plasma region in the vicinity of the target 5130. In the high-density plasma region, the deposition gas is ionized, so that an ion 5101 is generated. Examples of the ion 5101 include an oxygen cation (O⁺) and an argon cation (Ar⁺).

Here, the target 5130 has a polycrystalline structure which includes a plurality of crystal grains and in which a cleavage plane exists in at least one crystal grain. FIG. 38A shows a structure of an InGaZnO₄ crystal included in the target 5130 as an example. Note that FIG. 38A shows a structure of the case where the InGaZnO₄ crystal is observed from a direction parallel to the b-axis. FIG. 38A indicates that oxygen atoms in a Ga—Zn—O layer are positioned close to those in an adjacent Ga—Zn—O layer. The oxygen atoms have negative charge, whereby repulsive force is generated between the two adjacent Ga—Zn—O layers. As a result, the InGaZnO₄ crystal has a cleavage plane between the two adjacent Ga—Zn—O layers.

The ion 5101 generated in the high-density plasma region is accelerated toward the target 5130 side by an electric field, and then collides with the target 5130. At this time, a pellet 5100 a and a pellet 5100 b which are flat-plate-like (pellet-like) sputtered particles are separated and sputtered from the cleavage plane. Note that structures of the pellet 5100 a and the pellet 5100 b may be distorted by an impact of collision of the ion 5101.

The pellet 5100 a is a flat-plate-like (pellet-like) sputtered particle having a triangle plane, e.g., regular triangle plane. The pellet 5100 b is a flat-plate-like (pellet-like) sputtered particle having a hexagon plane, e.g., regular hexagon plane. Note that flat-plate-like (pellet-like) sputtered particles such as the pellet 5100 a and the pellet 5100 b are collectively called pellets 5100. The shape of a flat plane of the pellet 5100 is not limited to a triangle or a hexagon. For example, the flat plane may have a shape formed by combining two or more triangles. For example, a quadrangle (e.g., rhombus) may be formed by combining two triangles (e.g., regular triangles).

The thickness of the pellet 5100 is determined depending on the kind of deposition gas and the like. The thicknesses of the pellets 5100 are preferably uniform; the reason for this is described later. In addition, the sputtered particle preferably has a pellet shape with a small thickness as compared to a dice shape with a large thickness. For example, the thickness of the pellet 5100 is greater than or equal to 0.4 nm and less than or equal to 1 nm, preferably greater than or equal to 0.6 nm and less than or equal to 0.8 nm. In addition, for example, the width of the pellet 5100 is greater than or equal to 1 nm and less than or equal to 3 nm, preferably greater than or equal to 1.2 nm and less than or equal to 2.5 nm. The pellet 5100 corresponds to the initial nucleus in the description of (1) in FIG. 36. For example, when the ion 5101 collides with the target 5130 including an In—Ga—Zn oxide, the pellet 5100 that includes three layers of a Ga—Zn—O layer, an In—O layer, and a Ga—Zn—O layer as shown in FIG. 38B is separated. Note that FIG. 38C shows the structure of the separated pellet 5100 which is observed from a direction parallel to the c-axis. The pellet 5100 has a nanometer-sized sandwich structure including two Ga—Zn—O layers and an In—O layer.

The pellet 5100 may receive a charge when passing through the plasma, so that side surfaces thereof are negatively or positively charged. In the pellet 5100, for example, an oxygen atom positioned on its side surface may be negatively charged. When the side surfaces are charged with the same polarity, charges repel each other, and accordingly, the pellet 5100 can maintain a flat-plate (pellet) shape. In the case where a CAAC-OS is an In—Ga—Zn oxide, there is a possibility that an oxygen atom bonded to an indium atom is negatively charged. There is another possibility that an oxygen atom bonded to an indium atom, a gallium atom, or a zinc atom is negatively charged. In addition, the pellet 5100 may grow by being bonded with an indium atom, a gallium atom, a zinc atom, an oxygen atom, or the like when passing through plasma. A difference in size between (2) and (1) in FIG. 36 corresponds to the amount of growth in plasma. Here, in the case where the temperature of the substrate 5120 is at around room temperature, the pellet 5100 on the substrate 5120 hardly grows; thus, an nc-OS is formed (see FIG. 37B). An nc-OS can be deposited when the substrate 5120 has a large size because the deposition of an nc-OS can be carried out at room temperature. Note that in order that the pellet 5100 grows in plasma, it is effective to increase deposition power in sputtering. High deposition power can stabilize the structure of the pellet 5100.

As shown in FIGS. 37A and 37B, the pellet 5100 flies like a kite in plasma and flutters up to the substrate 5120. Since the pellets 5100 are charged, when the pellet 5100 gets close to a region where another pellet 5100 has already been deposited, repulsion is generated. Here, above the substrate 5120, a magnetic field in a direction parallel to the top surface of the substrate 5120 (also referred to as a horizontal magnetic field) is generated. A potential difference is given between the substrate 5120 and the target 5130, and accordingly, current flows from the substrate 5120 toward the target 5130. Thus, the pellet 5100 is given a force (Lorentz force) on the top surface of the substrate 5120 by an effect of the magnetic field and the current. This is explainable with Fleming's left-hand rule.

The mass of the pellet 5100 is larger than that of an atom. Therefore, to move the pellet 5100 over the top surface of the substrate 5120, it is important to apply some force to the pellet 5100 from the outside. One kind of the force may be force which is generated by the action of a magnetic field and current. In order to apply a sufficient force to the pellet 5100 so that the pellet 5100 moves over a top surface of the substrate 5120, it is preferable to provide, on the top surface, a region where the magnetic field in a direction parallel to the top surface of the substrate 5120 is 10 G or higher, preferably 20 G or higher, further preferably 30 G or higher, still further preferably 50 G or higher. Alternatively, it is preferable to provide, on the top surface, a region where the magnetic field in a direction parallel to the top surface of the substrate 5120 is 1.5 times or higher, preferably twice or higher, further preferably 3 times or higher, still further preferably 5 times or higher as high as the magnetic field in a direction perpendicular to the top surface of the substrate 5120.

At this time, the magnets and the substrate 5120 are moved or rotated relatively, whereby the direction of the horizontal magnetic field on the top surface of the substrate 5120 continues to change. Therefore, the pellet 5100 can be moved in various directions on the top surface of the substrate 5120 by receiving forces in various directions.

Furthermore, as shown in FIG. 37A, when the substrate 5120 is heated, resistance between the pellet 5100 and the substrate 5120 due to friction or the like is low. As a result, the pellet 5100 glides above the top surface of the substrate 5120. The glide of the pellet 5100 is caused in a state where its flat plane faces the substrate 5120. Then, when the pellet 5100 reaches the side surface of another pellet 5100 that has been already deposited, the side surfaces of the pellets 5100 are bonded. At this time, the oxygen atom on the side surface of the pellet 5100 is released. With the released oxygen atom, oxygen vacancies in a CAAC-OS might be filled; thus, the CAAC-OS has a low density of defect states. Note that the temperature of the top surface of the substrate 5120 is, for example, higher than or equal to 100° C. and lower than 500° C., higher than or equal to 150° C. and lower than 450° C., or higher than or equal to 170° C. and lower than 400° C. Hence, even when the substrate 5120 has a large size, it is possible to deposit a CAAC-OS.

Furthermore, the pellet 5100 is heated on the substrate 5120, whereby atoms are rearranged, and the structure distortion caused by the collision of the ion 5101 can be reduced. The pellet 5100 whose structure distortion is reduced is substantially single crystal. Even when the pellets 5100 are heated after being bonded, expansion and contraction of the pellet 5100 itself hardly occur, which is caused by turning the pellet 5100 into substantially single crystal. Thus, formation of defects such as a grain boundary due to expansion of a space between the pellets 5100 can be prevented, and accordingly, generation of crevasses can be prevented.

The CAAC-OS does not have a structure like a board of a single crystal oxide semiconductor but has arrangement with a group of pellets 5100 (nanocrystals) like stacked bricks or blocks. Furthermore, a grain boundary does not exist between the pellets 5100. Therefore, even when deformation such as shrink occurs in the CAAC-OS owing to heating during deposition, heating or bending after deposition, it is possible to relieve local stress or release distortion. Therefore, this structure is suitable for a flexible semiconductor device. Note that the nc-OS has arrangement in which pellets 5100 (nanocrystals) are randomly stacked.

When the target 5130 is sputtered with the ion 5101, in addition to the pellets 5100, zinc oxide or the like may be separated. The zinc oxide is lighter than the pellet 5100 and thus reaches the top surface of the substrate 5120 before the pellet 5100. As a result, the zinc oxide forms a zinc oxide layer 5102 with a thickness greater than or equal to 0.1 nm and less than or equal to 10 nm, greater than or equal to 0.2 nm and less than or equal to 5 nm, or greater than or equal to 0.5 nm and less than or equal to 2 nm. FIGS. 39A to 39D are cross-sectional schematic views.

As illustrated in FIG. 39A, a pellet 5105 a and a pellet 5105 b are deposited over the zinc oxide layer 5102. Here, side surfaces of the pellet 5105 a and the pellet 5105 b are in contact with each other. In addition, a pellet 5105 c is deposited over the pellet 5105 b, and then glides over the pellet 5105 b. Furthermore, a plurality of particles 5103 separated from the target together with the zinc oxide is crystallized by heat from the substrate 5120 to form a region 5105 a 1 on another side surface of the pellet 5105 a. Note that the plurality of particles 5103 may contain oxygen, zinc, indium, gallium, or the like.

Then, as illustrated in FIG. 39B, the region 5105 a 1 grows to part of the pellet 5105 a to form a pellet 5105 a 2. In addition, a side surface of the pellet 5105 c is in contact with another side surface of the pellet 5105 b.

Next, as illustrated in FIG. 39C, a pellet 5105 d is deposited over the pellet 5105 a 2 and the pellet 5105 b, and then glides over the pellet 5105 a 2 and the pellet 5105 b. Furthermore, a pellet 5105 e glides toward another side surface of the pellet 5105 c over the zinc oxide layer 5102.

Then, as illustrated in FIG. 39D, the pellet 5105 d is placed so that a side surface of the pellet 5105 d is in contact with a side surface of the pellet 5105 a 2. Furthermore, a side surface of the pellet 5105 e is in contact with another side surface of the pellet 5105 c. A plurality of particles 5103 separated from the target 5130 together with the zinc oxide is crystallized by heat from the substrate 5120 to form a region 5105 d 1 on another side surface of the pellet 5105 d.

As described above, deposited pellets are placed to be in contact with each other and then growth is caused at side surfaces of the pellets, whereby a CAAC-OS is formed over the substrate 5120. Therefore, each pellet of the CAAC-OS is larger than that of the nc-OS. A difference in size between (3) and (2) in FIG. 36 corresponds to the amount of growth after deposition.

When spaces between pellets are extremely small, the pellets may form a large pellet. The large pellet has a single crystal structure. For example, the size of the pellet may be greater than or equal to 10 nm and less than or equal to 200 nm, greater than or equal to 15 nm and less than or equal to 100 nm, or greater than or equal to 20 nm and less than or equal to 50 nm, when seen from the above. In this case, in an oxide semiconductor used for a minute transistor, a channel formation region might be fit inside the large pellet. That is, the region having a single crystal structure can be used as the channel formation region. Furthermore, when the size of the pellet is increased, the region having a single crystal structure can be used as the channel formation region, the source region, and the drain region of the transistor.

In this manner, when the channel formation region or the like of the transistor is formed in a region having a single crystal structure, the frequency characteristics of the transistor can be increased in some cases.

As shown in such a model, the pellets 5100 are considered to be deposited on the substrate 5120. Thus, a CAAC-OS can be deposited even when a formation surface does not have a crystal structure; therefore, a growth mechanism in this case is different from epitaxial growth. In addition, laser crystallization is not needed for formation of a CAAC-OS, and a uniform film can be formed even over a large-sized glass substrate or the like. For example, even when the top surface (formation surface) of the substrate 5120 has an amorphous structure (e.g., the top surface is formed of amorphous silicon oxide), a CAAC-OS can be formed.

In addition, it is found that in formation of the CAAC-OS, the pellets 5100 are arranged in accordance with the top surface shape of the substrate 5120 that is the formation surface even when the formation surface has unevenness. For example, in the case where the top surface of the substrate 5120 is flat at the atomic level, the pellets 5100 are arranged so that flat planes parallel to the a-b plane face downwards. In the case where the thickness of the pellets 5100 are uniform, a layer with a uniform thickness, flatness, and high crystallinity is formed. By stacking n layers (n is a natural number), the CAAC-OS can be obtained.

In the case where the top surface of the substrate 5120 has unevenness, a CAAC-OS in which n layers (n is a natural number) in each of which the pellets 5100 are arranged along the unevenness are stacked is formed. Since the substrate 5120 has unevenness, a gap is easily generated between the pellets 5100 in the CAAC-OS in some cases. Note that, even in such a case, owing to intermolecular force, the pellets 5100 are arranged so that a gap between the pellets is as small as possible even on the unevenness surface. Therefore, even when the formation surface has unevenness, a CAAC-OS with high crystallinity can be obtained.

Since a CAAC-OS is deposited in accordance with such a model, the sputtered particle preferably has a pellet shape with a small thickness. Note that when the sputtered particles have a dice shape with a large thickness, planes facing the substrate 5120 vary; thus, the thicknesses and orientations of the crystals cannot be uniform in some cases.

According to the deposition model described above, a CAAC-OS with high crystallinity can be formed even on a formation surface with an amorphous structure.

The structures, methods, and the like described in this embodiment can be used as appropriate in combination with any of the structures, methods, and the like described in the other embodiments and examples.

Embodiment 6

In this embodiment, an example of a semiconductor device (memory device) which includes a transistor of one embodiment of the present invention, which can hold stored data even when not powered, and which has an unlimited number of write cycles will be described with reference to drawings.

FIG. 20A is a cross-sectional view of a semiconductor device, and FIG. 20B is a circuit diagram of a memory cell 760 included in the semiconductor device.

The semiconductor device illustrated in FIGS. 20A and 20B includes a transistor 750 including a substrate 700 in a lower portion, and a transistor 200 including an oxide semiconductor and a capacitor 230 in an upper portion.

As the substrate 700, a single crystal semiconductor substrate or a polycrystalline semiconductor substrate of silicon or silicon carbide, a compound semiconductor substrate of silicon germanium, a silicon-on-insulator (SOI) substrate, or the like may be used. A transistor manufactured using a semiconductor substrate can operate at high speed easily.

In this embodiment, an example in which a p-type single crystal silicon substrate is used as the substrate 700 is described. The transistor 750 is a transistor whose channel is formed in the substrate 700. The transistor 750 includes a channel formation region 753, n-type impurity regions 754 functioning as lightly doped drain (LDD) regions or extension regions, n-type impurity regions 755 functioning as a source region and a drain region, a gate insulating film 752, and a gate electrode 751. The n-type impurity regions 755 have a higher impurity concentration than the n-type impurity regions 754. A side surface of the gate electrode 751 is provided with a sidewall insulating film 756. With the use of the gate electrode 751 and the sidewall insulating film 756 as masks, the n-type impurity regions 754 and the n-type impurity regions 755 can be formed in a self-aligned manner.

The transistor 750 is separated from other transistors 750 formed on the substrate 700 by an element separation region 789. Further, an insulating film 790 and an insulating film 791 are formed over and around the gate electrode 751 and the sidewall insulating film 756.

The gate electrode 103, a conductive film 203, and a conductive film 204 are formed over the insulating film 791. Note that the conductive film 203 is connected to the gate electrode 751 of the transistor 750.

An insulating film 205 is formed between the gate electrode 103, the conductive film 203, and conductive film 204. The insulating film 205 can be formed using a material similar to that of the gate insulating film 105 described in Embodiment 1 as appropriate.

An insulating film 206 that exposes part of the gate electrode 103, part of the conductive film 203, and part of the conductive film 204 is formed over the insulating film 205.

When an insulating film that has an effect of blocking water and hydrogen is used as the insulating film 206, water and hydrogen contained between the substrate 700 and the insulating film 206 can be prevented from diffusing into the oxide semiconductor film included in the transistor 200. As the insulating film 206, a single layer or a stacked layer including a material selected from aluminum oxide, aluminum oxynitride, silicon nitride, silicon nitride oxide, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, hafnium oxide, or tantalum oxide can be formed.

The gate insulating film 105 is formed over the gate electrode 103, the conductive film 203, the conductive film 204, and the insulating film 206. The electrode 113 h, which is one of a pair of electrode included in the transistor 200, is electrically connected to the conductive film 204 through an opening formed in the gate insulating film 105.

The transistor 200 that includes the gate electrode 103, the gate insulating film 105, the pair of electrodes 113 g and 113 h, and the gate electrode 119 is formed over the insulating film 791. Any of the transistors described in Embodiments 1 to 5 can be used as the transistor 200. Here, the transistor illustrated in FIG. 28 is employed as the transistor 200.

The insulating film 121 is formed over the transistor 200 and the insulating film 206. As the insulating film 121, the insulating film 121 described in Embodiment 1 can be used as appropriate.

The insulating film 123 is formed over the insulating film 121. The insulating film 123 can be formed using a material and a method similar to those of the insulating film 123 described in Embodiment 1. The plug 127 b is formed in an opening formed in the insulating film 123 and the insulating film 121. The plug 127 b is electrically connected to the electrode 113 h.

An insulating film 215 serving as a planarization insulating film is formed over the insulating film 123 and the plug 127 b. The insulating film 215 can be formed of a heat-resistant organic material, such as polyimide, acrylic, benzocyclobutene, polyamide, or epoxy. Other than such organic materials, it is possible to use a low-dielectric constant material (a low-k material), a siloxane-based resin, PSG (phosphosilicate glass), BPSG (borophosphosilicate glass), or the like. Note that the insulating film 215 may be formed by stacking a plurality of insulating films formed using these materials.

Note that the siloxane-based resin corresponds to a resin including a Si—O—Si bond formed using a siloxane-based material as a starting material. The siloxane-based resin may include as a substituent an organic group (e.g., an alkyl group or an aryl group) or a fluoro group. The organic group may include a fluoro group.

There is no particular limitation on the method for forming the insulating film 215, and any of the following methods can be used depending on the material: a sputtering method; an SOG method; spin coating; dipping; spray coating; a droplet discharging method (e.g., an ink-jet method); a printing method (e.g., screen printing, or offset printing); or the like. When the baking step of the insulating film 215 also serves as heat treatment for another layer, a semiconductor device can be manufactured efficiently.

The insulating film 215 may be formed using a material and a method similar to those of the insulating film 123 described in Embodiment 1 and then may be subjected to CMP treatment.

A plug 216 is formed over the insulating film 215 and electrically connected to the plug 127 b through an opening formed in the insulating film 215.

The gate electrode 751 is electrically connected to the conductive film 203. One of the n-type impurity regions 755 in the transistor 750 is electrically connected to a transistor 770 (see FIG. 20B), and the other thereof is electrically connected to a wiring SL (see FIG. 20B). Furthermore, the electrode 113 h is electrically connected to a wiring BL (see FIG. 20B), the electrode 113 g is electrically connected to a node FN (see FIG. 20B), the gate electrode 119 is electrically connected to a wiring WWL (see FIG. 20B), and the gate electrode 103 is electrically connected to a wiring BGL (see FIG. 20B).

Here, a semiconductor material of region in which a channel region of the transistor 750 is formed and a semiconductor material of a region in which a channel region of the transistor 200 is formed preferably have different band gaps. For example, in the case where an oxide semiconductor is used as the semiconductor material of the region in which the channel region of the transistor 200 is formed, it is preferable that a semiconductor material other than an oxide semiconductor be used as the semiconductor material of the region in which the channel region of the transistor 750 is formed. A transistor including a semiconductor material other than an oxide semiconductor, such as crystalline silicon, can operate at high speed more easily than a transistor including an oxide semiconductor. A transistor including an oxide semiconductor enables charges to be held for a long time owing to its electrical characteristics, that is, the low off-state current.

A transistor including crystalline silicon as a semiconductor material of a region in which a channel region of the transistor is formed can operate at higher speed than a transistor including an oxide semiconductor as a semiconductor material of a region in which a channel region is formed. By using this transistor as a reading transistor, data can be read at high speed.

Although both of the above transistors are n-channel transistors in the following description, it is needless to say that p-channel transistors can be used. Note that unless otherwise specified, the specific structure of the semiconductor device, such as a material used for the semiconductor device and the structure of the semiconductor device, need not be limited to that described here.

The transistor 200 is a transistor that includes an oxide semiconductor as a semiconductor material in a region in which a channel region is formed. Since the off-state current of the transistor 200 is low, stored data can be retained for a long period. In other words, power consumption can be sufficiently reduced because a semiconductor memory device in which refresh operation is unnecessary or the frequency of refresh operation is extremely low can be provided.

The transistor 200 and the capacitor 230 can be formed over the substrate over which the transistor 750 is formed as illustrated in FIG. 20A, which enables a higher degree of integration of the semiconductor device.

FIG. 20B illustrates the memory cell 760. The memory cell 760 includes the transistor 200, the transistor 750, the capacitor 230, and the transistor 770.

The transistor 200 includes an oxide semiconductor film in its channel formation region. Thus, the transistor 200 has an extremely small off-state current (extremely high off-state resistance). The transistor 200 is an n-channel or p-channel transistor. The following description is made on the case where the transistor 200 is an n-channel transistor. The transistor 200 is turned on when data is written, and accordingly is also referred to as a writing transistor. The transistor 200 may be an n-channel or p-channel transistor. The following description is made on the case where the transistor 101 is an n-channel transistor.

The transistor 200 has a dual-gate structure, and one of the gates is electrically connected to the wiring WWL. The wiring WWL can function as a write word line. The other gate is connected to the wiring BGL. Note that the other gate may be always kept at a constant potential.

One of a source and a drain of the transistor 200 is electrically connected to the wiring BL. The wiring BL can function as a bit line.

The other of the source and the drain of the transistor 200 is electrically connected to one electrode of the capacitor 230. The other electrode of the capacitor 230 is electrically connected to a wiring CL. The other of the source and the drain of the transistor 200 is electrically connected to a gate of the transistor 750.

By changing the potential of the wiring CL, the potential of the gate of the transistor 750 (the node FN) is changed. The wiring CL is also referred to as a capacitor line.

The transistor 750 is a p-channel transistor. Various materials such as an oxide semiconductor and silicon can be used for a channel formation region of the transistor 750. One of a source and a drain of the transistor 750 is electrically connected to one of a source and a drain of the transistor 770. The other of the source and the drain of the transistor 750 is electrically connected to the wiring SL.

The other of the source and the drain of the transistor 770 is electrically connected to the wiring BL. A gate of the transistor 770 is electrically connected to a wiring RWL. The transistor 770 is a transistor for electrically connecting the transistor 750 and the wiring BL when data is read, and is also referred to as a selection transistor.

The wiring SL can function as a source line or a power supply line. Although the wiring SL is preferably retained at a constant potential, the potential may be changed when power is stopped or supplied.

In the memory cell 760 in FIG. 20B, data is retained as the potential of the node FN. If the transistor 200 has sufficiently high off-state resistance, data can be retained for a very long period. Theoretically, a data retention period is determined depending on all capacitance between the node FN and each of other nodes (including the capacitance of the capacitor 230) and all resistance between the node FN and each of other nodes (including the off-state resistance of the transistor 200).

For example, when the capacitance is 30 fF and the resistance is 1×10²²Ω, the time constant is 9.5 years. Accordingly, after ten years, the difference between the potential of the node FN and a reference potential becomes lowered to approximately 35% of the difference between the initial potential and the reference potential. A reading method by which data reading is correctly performed even in such a case where the potential is lowered is required.

Operation for writing data to the memory cell 760 and operation for reading data from the memory cell 760 are described below with reference to FIG. 29. The threshold values of the transistors 750 and 770 are each lower than 0 and higher than −VDD.

<Writing Operation>

Data writing is performed by setting the potential of the wiring BL that is a bit line at the potential corresponding to the data when the transistor 200 is on. This method is basically the same as the method for data writing to a DRAM. The transistor 200 is different from the transistors 750 and 770 in the threshold value or the like; thus, here, when the transistor 200 is turned on, the potential of its gate (the potential of the wiring WWL) is set to V_(OS) _(—) _(H), and when the transistor 200 is turned off, the potential of its gate is set to V_(OS) _(—) _(L). Note that V_(OS) _(—) _(L) may be equal to GND (<VDD).

Here, when data “0” (one of two levels) is written, the potential of the wiring BL is set to GND, and when data “1” (the other of the two levels) is written, the potential of the wiring BL is set to VDD. At Time T1 in FIG. 29, the potential of the wiring WWL starts to increase, so that the transistor 200 is turned on. As a result, the node FN becomes to have a potential corresponding to data. For example, when data “0” is written, the potential of the node FN becomes GND, and when data “1” is written, the potential of the node FN becomes VDD. At Time T2, the potential of the wiring WWL starts to decrease, so that the transistor 200 is turned off, and writing is finished. When the transistor 200 is turned off, the potential of the node FN is slightly lowered by capacitive coupling between the gate of the transistor 200 (and the wiring WWL) and the node FN.

In writing, it is preferable that current do not flow between the wirings BL and SL. For example, the wirings BL and SL may have no potential difference. That is, as in the case of the wiring BL, the potential of the wiring SL may be changed in accordance with data.

In a more effective method, the potential of the wiring RWL is set to a potential at which the transistor 770 is turned off. The potentials of the wirings BL and SL are each higher than or equal to GND and lower than or equal to VDD. Accordingly, when the potential of the wiring RWL is set to VDD, the transistor 770 is turned off. The potential of the wiring SL remains VDD except in the standby period in this embodiment, but may be another potential.

<Retention Operation>

When data is retained, the transistor 200 is turned off. In FIG. 29, in a period from Time T3 to Time T4, data is retained with power supply stopped (standby period). In the standby period, all the wirings have the same potential (here, GND). In the case where the potential of the node FN is higher than GND at this time, the potential of the node FN is gradually lowered.

In the case where data “0” has been written, the potential of the node FN is close to GND; thus, its change does not become a significant problem. In contrast, in the case where data “1” has been written, the potential of the node ΔN is close to VDD at first, but is lowered over time. The potential decrease is ΔV. That is, the potential of the node FN (the potential of the gate of the transistor 750) is VDD−ΔV after the data retention period. Under the above conditions, the potential is lowered by approximately 10% in the case where the retention period is about one year, but is lowered to 35% of the initial potential in ten years as described above. In other words, ΔV=0.65×VDD. Here, when the potential decrease of the node FN is the largest after the period in which data retention is assured, the potential of the node FN becomes VDD−ΔV_(MAX).

<Reading Operation>

Data reading operation is performed by setting the potentials of the wiring BL and the wiring SL to different potentials, turning on the transistor 770, and determining whether current flows between the source and the drain of the transistor 750. Depending on the potential of the node FN, the conduction state of the transistor 750 varies, so that written data can be determined.

Specifically, the potential of the wiring RWL is set to an appropriate value (here, VDD), the transistor 770 is turned off, and the potential of the wiring SL is set to VDD. After the wiring BL is precharged to an appropriate potential (here, GND), the wiring BL is brought into a floating state. Then, the potential of the wiring CL is set to an appropriate value (here, α; note that GND<α<VDD).

In the case where data “0” has been written, although the potential of the node FN is close to GND right before this time, owing to the increase of the potential of the wiring CL from GND to α, the potential of the node FN becomes almost α because of capacitive coupling through the capacitor 230. In the case where data “1” has been written, the potential of the node FN becomes almost VDD−ΔV+α−GND. After that, the potential of the wiring RWL is set to an appropriate value (here, GND) at T5 to turn on the transistor 770.

In order that data is read correctly, in the case where data “0” has been written, it is required that the transistor 750 is on and the potential of the wiring BL increases from GND to VDD; in the case where data “1” has been written, it is required that the transistor 750 is off and the potential of the wiring BL remains GND.

To fulfill the requirements, the following two inequalities are required to be satisfied when the threshold value of the transistor 750 is Vth: α<VDD+Vth and VDD−ΔV+α−GND≧VDD+Vth. That is, GND+ΔV+Vth≦GND+ΔV_(MAX)+Vth≦α<VDD+Vth.

For example, 0.7[V]≦α<1.3 [V] is satisfied when VDD=+1.8 [V], GND=0 [V], Vth=−0.5 [V], and ΔV_(MAX)=1.2 [V]. Alternatively, 0.2 [V]≦α<0.5 [V] is satisfied when VDD=+0.9 [V], GND=0 [V], Vth=−0.4 [V], and ΔV_(MAX)=0.6 [V].

Note that α can be a given value in the required range, and a may be the average of VDD and GND (also referred to as VDD/2) or the sum of GND and the difference between VDD and GND that is divided by N (also referred to as VDD/N; note that N=3, 4, 5, . . . ). In the former case, VDD/2 is 0.9 [V]. In the latter case, VDD/3 is 0.3 [V]. Both values are in the required range.

As described above, in the case where the potential of the node FN is lowered from the initial potential by greater than or equal to 60% (in the case where the potential of the node FN is lowered to less than or equal to 40% of the initial potential) in the standby period, the potential of the node FN is preferably increased by increasing the potential of the wiring CL as appropriate in reading.

Note that although the written potential is initially VDD in the case of data “1”, the potential output to the wiring CL is GND. It needs to be noted that inverted data is output like this.

When including a transistor having a channel formation region formed using an oxide semiconductor and having an extremely low off-state current, the semiconductor device described in this embodiment can retain stored data for an extremely long time. In other words, refresh operation becomes unnecessary or the frequency of the refresh operation can be extremely low, which leads to a sufficient reduction in power consumption. Moreover, stored data can be retained for a long time even when power is not supplied (note that a potential is preferably fixed).

Furthermore, in the semiconductor device described in this embodiment, high voltage is not needed for writing data and there is no problem of deterioration of elements. Unlike in a conventional nonvolatile memory, for example, it is not necessary to inject and extract electrons into and from a floating gate; thus, a problem such as deterioration of a gate insulating film does not occur. That is, the semiconductor device of the disclosed invention does not have a limit on the number of times data can be rewritten, which is a problem of a conventional nonvolatile memory, and the reliability thereof is drastically improved. Furthermore, data is written depending on the state of the transistor (on or off), whereby high-speed operation can be easily achieved.

As described above, a miniaturized and highly integrated semiconductor device having high electrical characteristics can be provided.

The structures, methods, and the like described in this embodiment can be used as appropriate in combination with any of the structures, methods, and the like described in the other embodiments and examples.

Embodiment 7

In this embodiment, a structure example of a display device of one embodiment of the present invention is described.

Structure Example

FIG. 30A is a top view of the display device of one embodiment of the present invention. FIG. 30B is a circuit diagram illustrating a pixel circuit that can be used in the case where a liquid crystal element is used in a pixel in the display device of one embodiment of the present invention. FIG. 30C is a circuit diagram illustrating a pixel circuit that can be used in the case where an organic EL element is used in a pixel in the display device of one embodiment of the present invention.

The transistor in the pixel portion can be formed in accordance with the above embodiment. The transistor can be easily formed as an n-channel transistor, and thus part of a driver circuit that can be formed using an n-channel transistor can be formed over the same substrate as the transistor of the pixel portion. With the use of any of the transistors described in the above embodiments for the pixel portion or the driver circuit in this manner, a highly reliable display device can be provided.

FIG. 30A illustrates an example of a block diagram of an active matrix display device. A pixel portion 701, a first scan line driver circuit 702, a second scan line driver circuit 703, and a signal line driver circuit 704 are formed over a substrate 700 of the display device. In the pixel portion 701, a plurality of signal lines extended from the signal line driver circuit 704 are arranged and a plurality of scan lines extended from the first scan line driver circuit 702 and the second scan line driver circuit 703 are arranged. Note that pixels which include display elements are provided in a matrix in respective regions where the scan lines and the signal lines intersect with each other. The substrate 700 of the display device is connected to a timing control circuit (also referred to as a controller or a controller IC) through a connection portion such as a flexible printed circuit (FPC).

In FIG. 30A, the first scan line driver circuit 702, the second scan line driver circuit 703, and the signal line driver circuit 704 are formed over the substrate 700 where the pixel portion 701 is formed. Accordingly, the number of components which are provided outside, such as a driver circuit, can be reduced, so that a reduction in cost can be achieved. Furthermore, if the driver circuit is provided outside the substrate 700, wirings would need to be extended and the number of wiring connections would increase. When the driver circuit is provided over the substrate 700, the number of wiring connections can be reduced. Consequently, an improvement in reliability or yield can be achieved.

<Liquid Crystal Display Device>

FIG. 30B illustrates an example of a circuit configuration of the pixel. Here, a pixel circuit that can be used in a pixel of a VA liquid crystal display device is illustrated.

This pixel circuit can be applied to a structure in which one pixel includes a plurality of pixel electrodes. The pixel electrodes are connected to different transistors, and the transistors can be driven with different gate signals. Accordingly, signals applied to individual pixel electrodes in a multi-domain pixel can be controlled independently.

A gate wiring 712 of a transistor 716 and a gate wiring 713 of a transistor 717 are separated so that different gate signals can be supplied thereto. In contrast, a source or drain electrode 714 that functions as a data line is shared by the transistors 716 and 717. The transistor described in any of the above embodiments can be used as appropriate as each of the transistors 716 and 717. Thus, a highly reliable liquid crystal display device can be provided.

The shapes of a first pixel electrode electrically connected to the transistor 716 and a second pixel electrode electrically connected to the transistor 717 are described. The first pixel electrode and the second pixel electrode are separated by a slit. The first pixel electrode is spread in a V shape and the second pixel electrode is provided so as to surround the first pixel electrode.

A gate electrode of the transistor 716 is connected to the gate wiring 712, and a gate electrode of the transistor 717 is connected to the gate wiring 713. When different gate signals are supplied to the gate wiring 712 and the gate wiring 713, operation timings of the transistor 716 and the transistor 717 can be varied. As a result, alignment of liquid crystals can be controlled.

Further, a storage capacitor may be formed using a capacitor wiring 710, a gate insulating film functioning as a dielectric, and a capacitor electrode electrically connected to the first pixel electrode or the second pixel electrode.

The multi-domain pixel includes a first liquid crystal element 718 and a second liquid crystal element 719. The first liquid crystal element 718 includes the first pixel electrode, a counter electrode, and a liquid crystal layer therebetween. The second liquid crystal element 719 includes the second pixel electrode, a counter electrode, and a liquid crystal layer therebetween.

Note that a pixel circuit of the present invention is not limited to that shown in FIG. 30B. For example, a switch, a resistor, a capacitor, a transistor, a sensor, a logic circuit, or the like may be added to the pixel illustrated in FIG. 30B.

<Organic EL Display Device>

FIG. 30C illustrates another example of a circuit configuration of the pixel. Here, a pixel structure of a display device including an organic EL element is shown.

In an organic EL element, by application of voltage to a light-emitting element, electrons are injected from one of a pair of electrodes and holes are injected from the other of the pair of electrodes, into a layer containing a light-emitting organic compound; thus, current flows. The electrons and holes are recombined, and thus, the light-emitting organic compound is excited. The light-emitting organic compound returns to a ground state from the excited state, thereby emitting light. Owing to such a mechanism, this light-emitting element is referred to as a current-excitation light-emitting element.

FIG. 30C illustrates an applicable example of a pixel circuit. Here, one pixel includes two n-channel transistors. Note that an oxide semiconductor film of one embodiment of the present invention can be used for channel formation regions of the n-channel transistors. Further, digital time grayscale driving can be employed for the pixel circuit.

The configuration of the applicable pixel circuit and operation of a pixel employing digital time grayscale driving are described.

A pixel 720 includes a switching transistor 721, a driver transistor 722, a light-emitting element 724, and a capacitor 723. A gate electrode of the switching transistor 721 is connected to a scan line 726, a first electrode (one of a source electrode and a drain electrode) of the switching transistor 721 is connected to a signal line 725, and a second electrode (the other of the source electrode and the drain electrode) of the switching transistor 721 is connected to a gate electrode of the driver transistor 722. The gate electrode of the driver transistor 722 is connected to a power supply line 727 through the capacitor 723, a first electrode of the driver transistor 722 is connected to the power supply line 727, and a second electrode of the driver transistor 722 is connected to a first electrode (a pixel electrode) of the light-emitting element 724. A second electrode of the light-emitting element 724 corresponds to a common electrode 728. The common electrode 728 is electrically connected to a common potential line formed over the same substrate as the common electrode 728.

As the switching transistor 721 and the driver transistor 722, the transistor described in any of the above embodiments can be used as appropriate. In this manner, a highly reliable organic EL display device can be provided.

The potential of the second electrode (the common electrode 728) of the light-emitting element 724 is set to be a low power supply potential. Note that the low power supply potential is lower than a high power supply potential supplied to the power supply line 727. For example, the low power supply potential can be GND, 0 V, or the like. The high power supply potential and the low power supply potential are set to be higher than or equal to the forward threshold voltage of the light-emitting element 724, and the difference between the potentials is applied to the light-emitting element 724, whereby current is supplied to the light-emitting element 724, leading to light emission. The forward voltage of the light-emitting element 724 refers to a voltage at which a desired luminance is obtained, and includes at least a forward threshold voltage.

Note that gate capacitance of the driver transistor 722 may be used as a substitute for the capacitor 723, so that the capacitor 723 can be omitted. The gate capacitance of the driver transistor 722 may be formed between the channel formation region and the gate electrode.

Next, a signal input to the driver transistor 722 is described. In the case of a voltage-input voltage driving method, a video signal for sufficiently turning on or off the driver transistor 722 is input to the driver transistor 722. In order for the driver transistor 722 to operate in a linear region, voltage higher than the voltage of the power supply line 727 is applied to the gate electrode of the driver transistor 722. Note that voltage higher than or equal to voltage which is the sum of power supply line voltage and the threshold voltage Vth of the driver transistor 722 is applied to the signal line 725.

In the case of performing analog grayscale driving, a voltage higher than or equal to a voltage which is the sum of the forward voltage of the light-emitting element 724 and the threshold voltage Vth of the driver transistor 722 is applied to the gate electrode of the driver transistor 722. A video signal by which the driver transistor 722 is operated in a saturation region is input, so that current is supplied to the light-emitting element 724. In order for the driver transistor 722 to operate in a saturation region, the potential of the power supply line 727 is set higher than the gate potential of the driver transistor 722. When an analog video signal is used, it is possible to supply current to the light-emitting element 724 in accordance with the video signal and perform analog grayscale driving.

Note that the configuration of the pixel circuit of the present invention is not limited to that shown in FIG. 30C. For example, a switch, a resistor, a capacitor, a sensor, a transistor, a logic circuit, or the like may be added to the pixel circuit illustrated in FIG. 30C.

In the case where the transistor shown in any of the above embodiments is used for any of the circuits shown in FIGS. 30A to 30C, the source electrode (the first electrode) is electrically connected to the low potential side and the drain electrode (the second electrode) is electrically connected to the high potential side. Furthermore, the potential of the first gate electrode may be controlled by a control circuit or the like and the potential described above as an example, e.g., a potential lower than the potential applied to the source electrode, may be input to the second gate electrode through a wiring that is not illustrated.

For example, in this specification and the like, a display element, a display device which is a device including a display element, a light-emitting element, and a light-emitting device which is a device including a light-emitting element can employ a variety of modes or can include a variety of elements. A display element, a display device, a light-emitting element, or a light-emitting device includes, for example, at least one of an electroluminescence (EL) element (e.g., an EL element including organic and inorganic materials, an organic EL element, or an inorganic EL element), an LED (e.g., a white LED, a red LED, a green LED, or a blue LED), a transistor (a transistor that emits light depending on current), an electron emitter, a liquid crystal element, electronic ink, an electrophoretic element, a grating light valve (GLV), a plasma display panel (PDP), a display element using micro electro mechanical system (MEMS), a digital micromirror device (DMD), a digital micro shutter (DMS), MIRASOL (registered trademark), an interferometric modulator display (IMOD) element, a MEMS shutter display element, an optical-interference-type MEMS display element, an electrowetting element, a piezoelectric ceramic display, and a display element including a carbon nanotube. In addition, display media whose contrast, luminance, reflectivity, transmittance, or the like is changed by electrical or magnetic effect may be included. Examples of the display device including an EL element include an EL display. Examples of the display device including an electron emitter include a field emission display (FED) and an SED-type flat panel display (SED: surface-conduction electron-emitter display). Examples of the display device including a liquid crystal element include a liquid crystal display (e.g., a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct-view liquid crystal display, or a projection liquid crystal display). Examples of the display device including electronic ink, electronic liquid powder, or an electrophoretic element include electronic paper. In the case of a transflective liquid crystal display or a reflective liquid crystal display, some of or all of pixel electrodes function as reflective electrodes. For example, some or all of pixel electrodes are formed to contain aluminum, silver, or the like. In such a case, a memory circuit such as an SRAM can be provided under the reflective electrodes. Accordingly, power consumption can be further reduced.

At least part of this embodiment can be implemented in combination with any of the other embodiments described in this specification as appropriate.

Embodiment 8

In this embodiment, a display module including a semiconductor device of one embodiment of the present invention will be described with reference to FIG. 31.

In a display module 8000 illustrated in FIG. 31, a touch panel 8004 connected to an FPC 8003, a display panel 8006 connected to an FPC 8005, a backlight unit 8007, a frame 8009, a printed board 8010, and a battery 8011 are provided between an upper cover 8001 and a lower cover 8002. Note that the backlight unit 8007, the battery 8011, the touch panel 8004, and the like are not provided in some cases.

The semiconductor device of one embodiment of the present invention can be used for, for example, the display panel 8006.

The shapes and sizes of the upper cover 8001 and the lower cover 8002 can be changed as appropriate in accordance with the sizes of the touch panel 8004 and the display panel 8006.

The touch panel 8004 can be a resistive touch panel or a capacitive touch panel and can be formed to overlap with the display panel 8006. A counter substrate (sealing substrate) of the display panel 8006 can have a touch panel function. A photosensor may be provided in each pixel of the display panel 8006 to form an optical touch panel. An electrode for a touch sensor may be provided in each pixel of the display panel 8006 so that a capacitive touch panel is obtained.

The backlight unit 8007 includes a light source 8008. The light source 8008 may be provided at an end portion of the backlight unit 8007 and a light diffusing plate may be used.

The frame 8009 protects the display panel 8006 and also functions as an electromagnetic shield for blocking electromagnetic waves generated by the operation of the printed board 8010. The frame 8009 may function as a radiator plate.

The printed board 8010 is provided with a power supply circuit and a signal processing circuit for outputting a video signal and a clock signal. As a power source for supplying power to the power supply circuit, an external commercial power source or a power source using the battery 8011 provided separately may be used. The battery 8011 can be omitted in the case of using a commercial power source.

The display module 8000 may be additionally provided with a member such as a polarizing plate, a retardation plate, or a prism sheet.

The structure described in this embodiment can be used in appropriate combination with any of the structures described in the other embodiments.

Embodiment 9

In this embodiment, examples of an electronic device that uses a semiconductor device of one embodiment of the present invention will be described.

Specific examples of the electronic device that uses the semiconductor device of one embodiment of the present invention are as follows: display devices of televisions, monitors, and the like, lighting devices, desktop and laptop personal computers, word processors, image reproduction devices which reproduce still images and moving images stored in recording media such as digital versatile discs (DVDs), portable CD players, radios, tape recorders, headphone stereos, stereos, table clocks, wall clocks, cordless phone handsets, transceivers, mobile phones, car phones, portable game machines, tablet terminals, large game machines such as pachinko machines, calculators, portable information terminals, electronic notebooks, e-book readers, electronic translators, audio input devices, video cameras, digital still cameras, electric shavers, high-frequency heating appliances such as microwave ovens, electric rice cookers, electric washing machines, electric vacuum cleaners, water heaters, electric fans, hair dryers, air-conditioning systems such as air conditioners, humidifiers, and dehumidifiers, dishwashers, dish dryers, clothes dryers, futon dryers, electric refrigerators, electric freezers, electric refrigerator-freezers, freezers for preserving DNA, flashlights, electrical tools such as a chain saw, smoke detectors, and medical equipment such as dialyzers. Other examples are as follows: industrial equipment such as guide lights, traffic lights, conveyor belts, elevators, escalators, industrial robots, power storage systems, and power storage devices for leveling the amount of power supply and smart grid. In addition, moving objects and the like driven by fuel engines or electric motors using power from non-aqueous secondary batteries are also included in the category of electronic devices. Examples of the moving objects include electric vehicles (EV), hybrid electric vehicles (HEV) which include both an internal-combustion engine and a motor, plug-in hybrid electric vehicles (PHEV), tracked vehicles in which caterpillar tracks are substituted for wheels of these vehicles, motorized bicycles including motor-assisted bicycles, motorcycles, electric wheelchairs, golf carts, boats, ships, submarines, helicopters, aircrafts, rockets, artificial satellites, space probes, planetary probes, and spacecrafts.

FIG. 21A illustrates an example of a portable game console including a housing 901, a housing 902, a display portion 903, a display portion 904, a microphone 905, a speaker 906, an operation key 907, a stylus 908, and the like. Although the portable game machine in FIG. 21A has the two display portions 903 and 904, the number of display portions included in a portable game machine is not limited to this number. Any of the transistors described in Embodiments 1 to 4 can be used as transistors included in the display portions 903 and 904 and the like. Furthermore, any of the transistors described in Embodiments 1 to 4 can be used in a CPU, a memory device, or the like which is not illustrated in FIG. 21A.

FIG. 21B illustrates an example of a portable data terminal including a first housing 911, a second housing 912, a first display portion 913, a second display portion 914, a joint 915, an operation key 916, and the like. The first display portion 913 is provided in the first housing 911, and the second display portion 914 is provided in the second housing 912. The first housing 911 and the second housing 912 are connected to each other with the joint 915, and the angle between the first housing 911 and the second housing 912 can be changed with the joint 915. An image on the first display portion 913 may be switched depending on the angle between the first housing 911 and the second housing 912 at the joint 915. A display device with a position input function may be used as at least one of the first display portion 913 and the second display portion 914. Note that the position input function can be added by providing a touch panel in a display device. Alternatively, the position input function can be added by provision of a photoelectric conversion element called a photosensor in a pixel portion of a display device. Any of the transistors described in Embodiments 1 to 4 can be used as transistors included in the first display portion 913, the second display portion 914, and the like. Furthermore, any of the transistors described in Embodiments 1 to 4 can be used in a CPU, a memory device, or the like which is not illustrated in FIG. 21B.

FIG. 21C illustrates an example of a laptop personal computer, which includes a housing 921, a display portion 922, a keyboard 923, a pointing device 924, and the like. Any of the transistors described in Embodiments 1 to 4 can be used as transistors included in the display portion 922 and the like. Furthermore, any of the transistors described in Embodiments 1 to 4 can be used in a CPU, a memory device, or the like which is not illustrated in FIG. 21C.

FIG. 21D illustrates an example of an electric refrigerator-freezer including a housing 931, a door for a refrigerator 932, a door for a freezer 933, and the like. Any of the transistors described in Embodiments 1 to 4 can be used in a CPU, a memory device, or the like which is not illustrated in FIG. 21D.

FIG. 21E illustrates an example of a video camera, which includes a first housing 941, a second housing 942, a display portion 943, operation keys 944, a lens 945, a joint 946, and the like. The operation keys 944 and the lens 945 are provided for the first housing 941, and the display portion 943 is provided for the second housing 942. The first housing 941 and the second housing 942 are connected to each other with the joint 946, and the angle between the first housing 941 and the second housing 942 can be changed with the joint 946. Images displayed on the display portion 943 may be switched in accordance with the angle at the joint 946 between the first housing 941 and the second housing 942. Any of the transistors described in Embodiments 1 to 4 can be used as transistors included in the display portion 943 and the like. Furthermore, any of the transistors described in Embodiments 1 to 4 can be used in a CPU, a memory device, or the like which is not illustrated in FIG. 21E.

FIG. 21F illustrates an example of an automobile including a car body 951, wheels 952, a dashboard 953, lights 954, and the like. Any of the transistors described in Embodiments 1 to 4 can be used in a CPU, a memory device, or the like which is not illustrated in FIG. 21F.

This embodiment can be combined with any of the other embodiments described in this specification, as appropriate.

Example 1

This example shows results of calculating the concentration of injected oxygen in the depth direction of an oxide semiconductor film into which oxygen ions are injected. In this example, as the oxide semiconductor film to which oxygen ions are injected, the oxide semiconductor film 107 in contact with the gate insulating film 105 illustrated in FIGS. 1A to 1C is assumed.

For the calculation, a transport of ion in matter (TRIM) was used.

A sample used in this calculation has a structure in which a silicon oxide film and an oxide semiconductor film are sequentially stacked over a silicon wafer.

The silicon oxide film has an element atomic ratio of Si:O=1:2, a thickness of 100 nm, and a density of 2.2 g/cm³. The oxide semiconductor film is an IGZO film with an element atomic ratio of In:Ga:Zn:O=1:3:4:10, a thickness of 20 nm, and a density of 5.91 g/cm³. As the ion species, oxygen atomic ions with an atomic weight of 16 were used. The dose was 1×10¹⁶ ions/cm².

FIG. 22 shows the calculation results under the conditions where the acceleration voltage in injecting the ion species was 2.5 kV, 5 kV, and 7.5 kV. In FIG. 22, SiO₂ represents the silicon oxide film, and IGZO(134) represents the oxide semiconductor film.

In FIG. 22, the horizontal axis and the vertical axis indicate the depth direction and the concentration of oxygen, respectively. The solid line represents the calculation results of the case where the acceleration voltage was 2.5 kV, the broken line represents the calculation results of the case where the acceleration voltage was 5 kV, and the dashed-dotted line represents the calculation results of the case where the acceleration voltage was 7.5 kV.

These results show that controlling the acceleration voltage of the ion species and the thickness of the oxide semiconductor film allows the adjustment of the concentration of injected oxygen at the interface between the silicon oxide film and the oxide semiconductor film.

Example 2

This example shows results of measuring the concentration of injected oxygen in the depth direction of an oxide semiconductor film into which oxygen ions are injected. In this example, as the oxide semiconductor film to which oxygen ions are injected, the oxide semiconductor film 107 in contact with the gate insulating film 105 illustrated in FIGS. 1A to 1C is assumed.

<Fabrication Methods of Samples>

In this example, a sample A1 and a sample A2 each including the oxide semiconductor film included in the transistor of one embodiment of the present invention were fabricated.

<Sample A1>

The sample A1 was fabricated in such a manner that a silicon oxide film with a thickness of 100 nm was formed over a silicon wafer, a first oxide semiconductor film with a thickness of 20 nm was formed over the silicon oxide film, oxygen ions were injected to the first oxide semiconductor film, and a second oxide semiconductor film with a thickness of 50 nm was formed over the first oxide semiconductor film. Note that ¹⁸O⁺ atomic ions were injected to the sample A1.

The silicon oxide film was formed by a sputtering method.

The first oxide semiconductor film was formed by a sputtering method in such a manner that a sputtering target with an atomic ratio of In:Ga:Zn=1:3:4 was used, oxygen with a flow proportion of 11% was supplied as a sputtering gas into a reaction chamber of a sputtering apparatus, the pressure in the reaction chamber was adjusted to 0.7 Pa, and a direct-current power of 0.5 kW was supplied. The substrate temperature in forming the first oxide semiconductor film was set at 200° C.

Next, ¹⁸O⁺ atomic ions were added to the first oxide semiconductor film by an ion implantation method. At this time, the acceleration voltage and the dose were set at 5 kV and 1×10¹⁶ ions/cm², respectively.

Next, the second oxide semiconductor film was formed over the first oxide semiconductor film by a sputtering method in such a manner that a sputtering target with an atomic ratio of In:Ga:Zn=1:1:1 was used, oxygen with a flow proportion of 33% was supplied as a sputtering gas into a reaction chamber of a sputtering apparatus, the pressure in the reaction chamber was adjusted to 0.7 Pa, and a direct-current power of 0.5 kW was supplied. The substrate temperature in forming the first oxide semiconductor film was set at 300° C.

<Sample A2>

The sample A2 was fabricated in such a manner that a silicon oxide film with a thickness of 100 nm was formed over a silicon wafer, a first oxide semiconductor film with a thickness of 20 nm was formed over the silicon oxide film, oxygen ions were injected to the first oxide semiconductor film, and a second oxide semiconductor film with a thickness of 50 nm was formed over the first oxide semiconductor film. Note that ¹⁸O₂ ⁺ molecular ions were injected to the sample A2.

In the sample A2, ¹⁸O₂ ⁺ molecular ions, instead of oxygen atoms for the sample A1, were added to the first oxide semiconductor film by an ion implantation method. At this time, the acceleration voltage and the dose were set at 5 kV and 5×10¹⁵ ions/cm², respectively.

Next, the concentration of injected oxygen in the samples A1 and A2 in the depth direction was measured by SIMS. Note that the concentration of oxygen was measured from the silicon wafer side. The measurement results are shown in FIG. 23.

In FIG. 23, SiO₂ represents the silicon oxide film, IGZO(134) represents the first oxide semiconductor film, and IGZO(111) represents the second oxide semiconductor film. In FIG. 23, the horizontal axis and the vertical axis indicate the depth direction and the concentration of ¹⁸O⁺, respectively. On the horizontal axis, 0 nm is the interface between the silicon oxide film and the first oxide semiconductor film. Furthermore, the broken line represents the measurement results of the sample A1, and the solid line represents the measurement results of the sample A2. The concentration of ¹⁸O⁺ in the silicon oxide film is the concentration obtained according to the natural abundance of ¹⁸O (0.2%) contained in the silicon oxide film.

According to FIG. 23, ¹⁸O⁺ was injected to the silicon oxide film in the sample A1, but in contrast the concentration of ¹⁸O⁺ injected to the silicon oxide film in the sample A2 was very low. It can be found from these results that oxygen atomic ions can be injected to a shallower region in the case of using oxygen molecular ions than the case of using oxygen atomic ions.

Example 3

This example shows results of measuring the concentration of injected oxygen in the depth direction of an oxide semiconductor film that is subjected to injection of oxygen ions and heat treatment. In this example, as the oxide semiconductor film to which oxygen ions are injected, the oxide semiconductor film 107 in contact with the gate insulating film 105 illustrated in FIGS. 1A to 1C is assumed.

<Fabrication Methods of Samples>

In this example, the sample A2 fabricated in Example 2 and samples B1 to B3 that are each obtained by performing heat treatment on the sample A2 were fabricated.

<Sample B1>

After forming the sample A2 in the manner described in Example 2, heat treatment was performed at 450° C. in a nitrogen atmosphere for 1 hour, and then heat treatment was performed at 450° C. in an oxygen atmosphere for 1 hour.

<Sample B2>

After forming the sample A2 in the manner described in Example 2, heat treatment was performed at 500° C. in a nitrogen atmosphere for 1 hour, and then heat treatment was performed at 500° C. in an oxygen atmosphere for 1 hour.

<Sample B3>

After forming the sample A2 in the manner described in Example 2, heat treatment was performed at 550° C. in a nitrogen atmosphere for 1 hour, and then heat treatment was performed at 550° C. in an oxygen atmosphere for 1 hour.

Next, the concentration of injected ¹⁸O⁺ in the sample A2 and the samples B1 to B3 in the depth direction was measured by SIMS. Note that the concentration of oxygen was measured from the silicon wafer side. The measurement results are shown in FIG. 24.

In FIG. 24, SiO₂ represents the silicon oxide film, IGZO(134) represents the first oxide semiconductor film, and IGZO(111) represents the second oxide semiconductor film. In FIG. 24, the horizontal axis and the vertical axis indicate the depth direction and the concentration of ¹⁸O⁺, respectively. On the horizontal axis, 0 nm is the interface between the silicon oxide film and the first oxide semiconductor film. Furthermore, the broken line represents the measurement results of the sample A2, the thin solid line represents the measurement results of the sample B1, the thick solid line represents the measurement results of the sample B2, and the dashed-dotted line represents the measurement results of the sample B3. The concentration of ¹⁸O⁺ in the silicon oxide film is the concentration obtained according to the natural abundance of ¹⁸O (0.2%) contained in the silicon oxide film.

According to FIG. 24, in the samples B1 to B3, when the temperature of the heat treatment was higher, a larger amount of ¹⁸O⁺ injected to the first oxide semiconductor film diffused to the second oxide semiconductor film.

These results show that oxygen contained in the first oxide semiconductor film can be diffused into the second oxide semiconductor film by performing the steps of adding oxygen to the first oxide semiconductor film, forming the second oxide semiconductor film over the first oxide semiconductor film, and performing heat treatment.

Example 4

This example shows results of measuring electrical characteristics of the transistor included in the memory cell described in Embodiment 6 with reference to FIGS. 20A and 20B.

<Method for Manufacturing Transistor>

First, the steps for manufacturing a transistor are described. Here, as a typical method, a method for manufacturing the transistor 200 included in the memory cell is described. The details of the structure of the transistor 200 illustrated in FIGS. 20A and 20B are described with reference to FIG. 28. In this example, the method for manufacturing the transistor is described with reference to FIGS. 2A to 2D, FIGS. 3A to 3C, FIGS. 7A to 7C, and FIG. 28.

As illustrated in FIG. 2A, an insulating film (not illustrated) was formed over the substrate 101, and the gate electrode 103 was formed over the insulating film. Next, the insulating film 104 was formed over the insulating film and the gate electrode 103, and the oxide semiconductor film 106 was formed over the insulating film 104. Next, the oxygen 108 was added to the oxide semiconductor film 106, so that the oxide semiconductor film 106 a to which oxygen was added was formed as illustrated in FIG. 2B.

A silicon wafer was used as the substrate 101.

The substrate 101 was heated at 950° C. in an oxygen atmosphere containing hydrogen chloride, so that a 400-nm-thick silicon oxide film containing chlorine was formed on the surface of the substrate 101.

Furthermore, a 50-nm-thick In—Ga—Zn oxynitride film was formed by a sputtering method over the insulating film, a mask was formed over the In—Ga—Zn oxynitride film by a lithography process, and the In—Ga—Zn oxynitride film was selectively etched, so that the gate electrode 103 was formed. Then, the mask was removed.

The sputtering conditions used for forming the In—Ga—Zn oxynitride film were as follows: an In—Ga—Zn—O target with a ratio of In:Ga:Zn=1:1:1 was used, nitrogen as a sputtering gas was introduced to a chamber at a pressure of 40 Pa, the substrate temperature was set at 500° C., and the power supply was 0.5 kW.

As the insulating film 104, a silicon oxynitride film with a thickness of 100 nm was formed by a plasma CVD method.

As the oxide semiconductor film 106, a 20-nm-thick In—Ga—Zn oxide film was formed by a sputtering method. The sputtering conditions at this time were as follows: a target with a ratio of In:Ga:Zn=1:3:4 was used, oxygen was introduced as a sputtering gas at a flow proportion of 11% into a chamber having a pressure of 0.7 Pa, the substrate temperature was 200° C., and the supplied electric power was 0.5 kW.

Oxygen molecular ions were added as the oxygen 108 by an ion implantation method with a dose of 1×10¹⁶ ions/cm² at an acceleration voltage of 5 kV.

Next, as illustrated in FIG. 2B, the oxide semiconductor film 109 was formed over the oxide semiconductor film 106 a to which oxygen was added.

As the oxide semiconductor film 109, a 20-nm-thick In—Ga—Zn oxide film was formed by a sputtering method. The sputtering conditions at this time were as follows: a target with a ratio of In:Ga:Zn=1:1:1 was used, oxygen was introduced as a sputtering gas at a flow proportion of 33% into a chamber having a pressure of 0.7 Pa, the substrate temperature was 300° C., and the power supply was 0.5 kW.

Then, heat treatment was performed so that part of oxygen contained in the oxide semiconductor film 106 a was transferred to the oxide semiconductor film 109, so that the oxide semiconductor film 106 b and the oxide semiconductor film 109 a in which oxygen vacancies were reduced were formed as illustrated in FIG. 2C.

Here, heat treatment was performed at 450° C. in a nitrogen atmosphere for 1 hour, and after that, another heat treatment was performed at 450° C. in an oxygen atmosphere for 1 hour.

Next, as illustrated in FIG. 7A, the conductive film 112 was formed over the oxide semiconductor film 109 a.

Here, as the conductive film 112, a 50-nm-thick tungsten film was formed by a sputtering method.

Next, a mask was formed over the conductive film 112 by a lithography process, and then the insulating film 104, the oxide semiconductor film 106 a, the oxide semiconductor film 109 a, and the conductive film 112 were etched; thus, the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 110, and the conductive film 113 were formed as illustrated in FIG. 7B.

Next, a mask was formed over the gate insulating film 105, the oxide semiconductor film 107, the oxide semiconductor film 110, and the conductive film 113 by a lithography process, and part of the gate insulating film 105 was etched to expose part of the gate electrode 751 of the transistor 750 illustrated in FIG. 20B. Then, as illustrated in FIG. 28, the pair of electrodes 113 g and 113 h was formed. Furthermore, the conductive film 113 was etched to form the pair of electrodes 113 c and 113 d. At this time, the oxide semiconductor film 111 was formed.

Here, the pair of electrodes 113 g and 113 h was formed in such a manner that a 70-nm-thick tungsten film was formed by a sputtering method, a mask was formed over the tungsten film by a lithography process, and then the tungsten film was selectively etched. Then, the mask was removed.

Next, an oxide semiconductor film, an insulating film, and a conductive film were stacked over the pair of electrodes 113 a and 113 b and the oxide semiconductor film 111. Then, a mask was formed over the conductive film by a lithography process, and the oxide semiconductor film, the insulating film, and the conductive film were etched to form the oxide semiconductor film 115, the gate insulating film 117, and the gate electrode 119 as illustrated in FIG. 28.

As the oxide semiconductor film to be processed into the oxide semiconductor film 115, a 5-nm-thick In—Ga—Zn-based oxide film was formed by a sputtering method. As for sputtering conditions at this time, a target of In:Ga:Zn=1:3:2 was used, oxygen was introduced as a sputtering gas at a flow proportion of 33% into a chamber having a pressure of 0.4 Pa; the substrate temperature was 200° C., and the power suppy was 0.5 kW.

As the insulating film to be processed into the gate insulating film 117, a 20-nm-thick silicon oxynitride film was formed by a plasma CVD method.

As the conductive film to be processed into the gate electrode 119, a 30-nm-thick titanium nitride film and a 135-nm-thick tungsten film were stacked by a sputtering method.

Next, the insulating film 121 was formed, and heat treatment was performed to form the insulating film 123.

As the insulating film 121, a 150-nm-thick aluminum oxide film was formed by a sputtering method.

The heat treatment was performed under the following conditions: 450° C., an oxygen atmosphere, and 1 hour.

As the insulating film 123, a 300-nm-thick silicon oxynitride film was formed by a plasma CVD method.

Next, a mask was formed over the insulating film 121 and the insulating film 123 by a lithography process, part of the insulating film 121 and part of the insulating film 123 are etched to expose part of the pair of electrodes 113 a and 113 b, and the plugs 127 a and 127 b illustrated in FIG. 28 were formed.

Here, as the plugs 127 a and 127 b, a 50-nm-thick titanium film, a 200-nm-thick aluminum film, and a 50-nm-thick titanium film were stacked by a sputtering method.

Through the above-described steps, the transistor was fabricated. The channel length and the channel width of the transistor were 0.8 μm and 0.8 μm, respectively.

<Measurement Results of Electrical Characteristics>

Next, electrical characteristics of the transistor were measured. First, electrical characteristics before the stress test (hereinafter referred to as initial characteristics) were measured. Here, a change in characteristics of the source-drain current (hereinafter referred to as the drain current), that is, I_(d)−V_(g) characteristics were measured under the conditions where the voltage between the source and the drain (hereinafter referred to as the drain voltage) was 0.1 V and 1.8 V, and the voltage between the source and the gate (hereinafter referred to as the gate voltage) was changed from −3 V to +3 V. FIG. 25A shows the results thereof.

Next, the stress test was performed on the transistor. Here, a BT stress test was performed on the memory cell 760 described in Embodiment 6 with reference to FIGS. 20A and 20B.

A measurement method of the gate BT stress test, which is one kind of the BT stress test, is described. First, the substrate temperature was kept constant at given temperature (hereinafter, referred to as stress temperature) to measure the initial I_(d)−V_(g) characteristics of the transistor.

Next, while the substrate temperature was kept at the stress temperature, the pair of electrodes serving as a source electrode and a drain electrode of the transistor was set at the same potential to each other and the gate electrode was supplied with a potential different from that of the pair of electrodes for a certain period of time (hereinafter referred to as stress time). Then, the I_(d)−V_(g) characteristics of the transistor were measured while the substrate temperature was kept at the stress temperature. As a result, a difference in threshold voltage and a difference in shift value in the I_(d)−V_(g) characteristics between before and after the gate BT stress test can be obtained as the amount of change.

The stress test in which the pair of electrodes serving as a source electrode and a gate electrode of the transistor were set at the same potential and the drain electrode was supplied with a potential different from that of the pair of electrodes for a certain period of time is referred to as the drain BT stress test.

Here, a stress test corresponding to the retention operation of data “1” or “0” was performed. Note that the voltages applied to the wirings in FIG. 20B in the writing operation of the data “1” or “0” and the retention operation of the data “1” or “0” are shown in Table 1.

TABLE 1 Writing Retention Voltage Data “1” Data “0” Data “1” Data “0” WWL (V) +3.3 +3.3 0 0 BL (V) +1.8 0 0 0 FN (V) 0 or +1.8 +1.8 0 BGL (V) −5

Since the retention operation subjects the transistor 200 to more stress than the writing operation in the memory cell 760, the stress test corresponding to the retention operation was performed here.

As shown in Table 1, in the transistor 200 illustrated in FIGS. 20A and 20B, a negative voltage was applied to the gate electrode 103 that was connected to the wiring BGL in the retention operation of the data “1”. The stress test under this state is referred to as −BGBT in the description below. Moreover, a positive voltage was applied to the electrode 113 g that was connected to the node FN. The stress test under this state is referred to as +DBT below.

In the case of the retention operation of the data “0”, a negative voltage was applied to the gate electrode 103 that was connected to the wiring BGL. The stress test under this state is referred to as −BGBT in the description below.

The stress test −BGBT and +DBT assuming the retention operation of the data “1” was performed under the conditions where the voltage (V_(g)) of the gate electrode 119 of the transistor 200 illustrated in FIGS. 20A and 20B was 0 V, the voltage (V_(d)) of the electrode 113 g was +1.8 V, the voltage (V_(s)) of the electrode 113 h was 0 V, the voltage (V_(bg)) of the gate electrode 103 was −5 V, the substrate temperature was 85° C., and the stress time was 1 hour. After the stress test, I_(d)−V_(g) characteristics of the transistor were measured. The initial characteristics and the I_(d)−V_(g) characteristics after the stress test are shown in FIG. 25B.

The stress test −BGBT assuming the retention operation of the data “0” was performed under the conditions where the voltage (V_(g)) of the gate electrode 119 of the transistor 200 illustrated in FIGS. 20A and 20B was 0 V, the voltage (V_(d)) of the electrode 113 g was 0 V, the voltage (V_(s)) of the electrode 113 h was 0 V, the voltage (V_(bg)) of the gate electrode 103 was −5 V, the substrate temperature was 85° C., and the stress time was 1 hour. After the stress test, I_(d)−V_(g) characteristics of the transistor were measured. The initial characteristics and the I_(d)−V_(g) characteristics after the stress test are shown in FIG. 25C.

FIG. 26 shows a variation in threshold voltage (ΔV_(th)) and a variation in the shift value (ΔShift) in each of the stress test assuming the retention operation of the data “1” and the stress test assuming the retention operation of the data “0”.

The threshold voltage and the shift value in this specification will be described. The threshold voltage (V_(th)) is defined as, in the I_(d)−V_(g) curve where the horizontal axis represents gate voltage (V_(g) [V]) and the vertical axis represents the square root of drain current I_(d) (I_(d) ^(1/2) [A^(1/2)]), gate voltage at the intersection point of the line of I_(d) ^(1/2)=0 (V_(g) axis) and the tangent to the curve at a point where the slope of the curve is the steepest. Note that here, the threshold voltage was calculated with a drain voltage V_(d) of +1.8 V.

Furthermore, the shift value (Shift) in this specification is defined as, in the I_(d)−V_(g) curve where the horizontal axis represents the gate voltage (V_(g) [V]) and the vertical axis represents the logarithm of the drain current (I_(d) [A]), gate voltage at the intersection point of the line of I_(d)=1.0×10⁻¹² [A] and the tangent to the curve at a point where the slope of the curve is the steepest. Note that here, the shift value was calculated with a drain voltage V_(d) of +1.8 V.

In FIGS. 25A to 25C, the horizontal axis represents the gate voltage, and the vertical axis represents the drain current. In FIG. 25A, the number of transistors is 25. In FIGS. 25B and 25C, initial characteristics of the transistors are represented by broken lines, and I_(d)−V_(g) characteristics after the stress test of the transistors are represented by solid lines.

According to FIG. 25A, normally-off characteristics were obtained. Furthermore, FIGS. 25B and 25C and FIG. 26 show that variations in threshold voltage and shift value by the stress test were small.

Example 5

This example shows results of calculating the concentration of injected oxygen in the depth direction of an oxide semiconductor film into which oxygen ions are injected. In this example, as the oxide semiconductor film to which oxygen ions are injected, the oxide semiconductor film 115 in contact with the gate insulating film 117 illustrated in FIGS. 1A to 1C is assumed.

For the calculation, a TRIM was used.

A sample used in this calculation has a structure in which a silicon oxide film, a first oxide semiconductor film, a second oxide semiconductor film, and a third oxide semiconductor film are sequentially stacked over a silicon wafer.

The silicon oxide film has an element atomic ratio of Si:O=1:2, a thickness of 100 nm, and a density of 2.2 g/cm³. The first oxide semiconductor film is an IGZO film with an element atomic ratio of In:Ga:Zn:O=1:3:4:10, a thickness of 20 nm, and a density of 5.91 g/cm³. The second oxide semiconductor film is an IGZO film with an element atomic ratio of In:Ga:Zn:O=1:1:1:4, a thickness of 15 nm, and a density of 6.24 g/cm³. The third oxide semiconductor film is an IGZO film with an element atomic ratio of In:Ga:Zn:O=1:3:2:8, a thickness of 5 nm, and a density of 5.71 g/cm³. As the ion species, oxygen atomic ions with an atomic weight of 16 were used. The dose was 1×10¹⁶ ions/cm².

FIG. 27 shows the calculation results under the conditions where the acceleration voltage in injecting the ion species was 2.5 kV, 5 kV, 7.5 kV, 10 kV, and 15 kV. In FIG. 27, SiO₂ represents the silicon oxide film, IGZO(134) represents the first oxide semiconductor film, IGZO(111) represents the second oxide semiconductor film, and IGZO(132) represents the third oxide semiconductor film.

In FIG. 27, the horizontal axis and the vertical axis indicate the depth direction and the concentration of oxygen, respectively. The thin solid line represents the calculation results of the case where the acceleration voltage was 2.5 kV, the thin broken line represents the calculation results of the case where the acceleration voltage was 5 kV, and the thin dashed-dotted line represents the calculation results of the case where the acceleration voltage was 7.5 kV. The thick solid line represents the calculation results of the case where the acceleration voltage was 10 kV, and the thick broken line represents the calculation results of the case where the acceleration voltage was 15 kV.

These results show that controlling the acceleration voltage of the ion species and the thickness of the oxide semiconductor film allows the adjustment of the concentration of injected oxygen at the interface between the silicon oxide film and the oxide semiconductor film. Furthermore, as shown in Examples 1 to 4, by adjusting the concentration of injected oxygen at the interface between the silicon oxide film and the oxide semiconductor film, a transistor with small variations in threshold voltage and the shift value can be formed.

This application is based on Japanese Patent Application serial no. 2013-264391 filed with Japan Patent Office on Dec. 20, 2013, the entire contents of which are hereby incorporated by reference. 

What is claimed is:
 1. A method for manufacturing a semiconductor device, comprising the steps of: forming a first gate electrode; forming a first insulating film over the first gate electrode; forming a first oxide semiconductor film over the first insulating film; adding oxygen to the first oxide semiconductor film; forming a second oxide semiconductor film over the first oxide semiconductor film after adding the oxygen; performing a heat treatment on the first oxide semiconductor film and the second oxide semiconductor film; etching a part of the first insulating film, a part of the first oxide semiconductor film, and a part of the second oxide semiconductor film to form a first gate insulating film having a projection after performing the heat treatment; forming a pair of electrodes in contact with the second oxide semiconductor film after etching the part of the second oxide semiconductor film; forming a third oxide semiconductor film over the second oxide semiconductor film and the pair of electrodes; forming a second gate insulating film over the third oxide semiconductor film; and forming a second gate electrode over the second gate insulating film.
 2. The method for manufacturing a semiconductor device according to claim 1, wherein the oxygen is added to the first oxide semiconductor film by an ion implantation method, an ion doping method, or plasma treatment.
 3. The method for manufacturing a semiconductor device according to claim 1, wherein the first oxide semiconductor film, the second oxide semiconductor film, and the third oxide semiconductor film include indium or gallium.
 4. The method for manufacturing a semiconductor device according to claim 1, wherein conduction band minimums of the first oxide semiconductor film and the third oxide semiconductor film are closer to a vacuum level than a conduction band minimum of the second oxide semiconductor film is.
 5. The method for manufacturing a semiconductor device according to claim 1, wherein a difference in energy level between a conduction band minimum of the second oxide semiconductor film and each of conduction band minimums of the first oxide semiconductor film and the third oxide semiconductor film is greater than or equal to 0.05 eV and less than or equal to 2 eV.
 6. The method for manufacturing a semiconductor device according to claim 1, further comprising a step of forming a second insulating film under the first gate electrode and the first insulating film, wherein the second insulating film is in contact with the pair of electrodes.
 7. The method for manufacturing a semiconductor device according to claim 1, wherein the second oxide semiconductor film includes a low resistance region, and wherein each of the pair of electrodes includes a region having high oxygen concentration.
 8. A method for manufacturing a semiconductor device, comprising the steps of: forming a first gate electrode; forming a first insulating film over the first gate electrode; forming a first oxide semiconductor film over the first insulating film; forming a second oxide semiconductor film over the first oxide semiconductor film; etching a part of the first insulating film, a part of the first oxide semiconductor film, and a part of the second oxide semiconductor film to form a first gate insulating film having a projection; forming a pair of electrodes in contact with the second oxide semiconductor film after etching the part of the second oxide semiconductor film; forming a third oxide semiconductor film over the second oxide semiconductor film and the pair of electrodes; adding oxygen to the third oxide semiconductor film; performing a heat treatment on the third oxide semiconductor film after adding the oxygen; forming a second gate insulating film over the third oxide semiconductor film after performing the heat treatment; and forming a second gate electrode over the second gate insulating film.
 9. The method for manufacturing a semiconductor device according to claim 8, wherein the oxygen is added to the third oxide semiconductor film by an ion implantation method, an ion doping method, or plasma treatment.
 10. The method for manufacturing a semiconductor device according to claim 8, wherein the first oxide semiconductor film, the second oxide semiconductor film, and the third oxide semiconductor film include indium or gallium.
 11. The method for manufacturing a semiconductor device according to claim 8, wherein conduction band minimums of the first oxide semiconductor film and the third oxide semiconductor film are closer to a vacuum level than a conduction band minimum of the second oxide semiconductor film is.
 12. The method for manufacturing a semiconductor device according to claim 8, wherein a difference in energy level between a conduction band minimum of the second oxide semiconductor film and each of conduction band minimums of the first oxide semiconductor film and the third oxide semiconductor film is greater than or equal to 0.05 eV and less than or equal to 2 eV.
 13. The method for manufacturing a semiconductor device according to claim 8, further comprising a step of forming a second insulating film under the first gate electrode and the first insulating film, wherein the second insulating film is in contact with the pair of electrodes.
 14. The method for manufacturing a semiconductor device according to claim 8, wherein the second oxide semiconductor film includes a low resistance region, and wherein each of the pair of electrodes includes a region having high oxygen concentration.
 15. A method for manufacturing a semiconductor device, comprising the steps of: forming a first gate electrode; forming a first insulating film over the first gate electrode; forming a first oxide semiconductor film over the first insulating film; adding oxygen to the first oxide semiconductor film; forming a second oxide semiconductor film over the first oxide semiconductor film after adding the oxygen to the first oxide semiconductor film; performing a first heat treatment on the first oxide semiconductor film and the second oxide semiconductor film; etching a part of the first insulating film, a part of the first oxide semiconductor film, and a part of the second oxide semiconductor film to form a first gate insulating film having a projection after performing the first heat treatment; forming a pair of electrodes in contact with the second oxide semiconductor film after etching the part of the second oxide semiconductor film; forming a third oxide semiconductor film over the second oxide semiconductor film and the pair of electrodes; adding oxygen to the third oxide semiconductor film; performing a second heat treatment on the third oxide semiconductor film after adding the oxygen to the third oxide semiconductor film; forming a second gate insulating film over the third oxide semiconductor film after performing the second heat treatment; and forming a second gate electrode over the second gate insulating film.
 16. The method for manufacturing a semiconductor device according to claim 15, wherein the oxygen is added to the first oxide semiconductor film and the third oxide semiconductor film by an ion implantation method, an ion doping method, or plasma treatment.
 17. The method for manufacturing a semiconductor device according to claim 15, wherein the first oxide semiconductor film, the second oxide semiconductor film, and the third oxide semiconductor film include indium or gallium.
 18. The method for manufacturing a semiconductor device according to claim 15, wherein conduction band minimums of the first oxide semiconductor film and the third oxide semiconductor film are closer to a vacuum level than a conduction band minimum of the second oxide semiconductor film is, and wherein a difference in energy level between the conduction band minimum of the second oxide semiconductor film and each of the conduction band minimums of the first oxide semiconductor film and the third oxide semiconductor film is greater than or equal to 0.05 eV and less than or equal to 2 eV.
 19. The method for manufacturing a semiconductor device according to claim 15, further comprising a step of forming a second insulating film under the first gate electrode and the first insulating film, wherein the second insulating film is in contact with the pair of electrodes.
 20. The method for manufacturing a semiconductor device according to claim 15, wherein the second oxide semiconductor film includes a low resistance region, and wherein each of the pair of electrodes includes a region having high oxygen concentration. 